Updated on 2022/10/01

写真a

 
NISHIHARA Yasushi
 
Organization
Research Institute for Interdisciplinary Science Professor
Position
Professor
Profile
[最終学歴] 総合研究大学院大学 数物科学研究科 博士後期課程 中退 (1996年)
[学位]博士(理学) 総合研究大学院大学 (1997年) (指導教員:高橋 保 先生)
[担当授業科目](学部)
前期:有機化学 1-2,化学実験 1(分担),自然科学入門(分担)
後期:有機化学 7-8, 化学実験 2(分担),化学ゼミナールB(分担)
(大学院前期課程) 後期:有機金属触媒化学
(大学院後期課程) 前期:合成有機分子化学,動態機能化学演習
[専門分野]有機合成化学,有機金属化学,高分子化学,有機材料化学
[キーワード]遷移金属触媒,有機薄膜太陽電池,有機電界効果トランジスタ,結合の活性化,有機ホウ素化学,有機ケイ素化学,有機フッ素化学
[所属学会] 日本化学会,有機合成化学協会,高分子学会,錯体化学会,近畿化学協会,ケイ素化学協会,アメリカ化学会,応用物理学会
[研究内容] 有機金属錯体触媒を利用した新規有機合成反応の開発と機能性材料への応用
[研究の目標] これまでにない活性や選択性を発現するような新規な有機金属錯体触媒を設計,合成し,新規かつ高選択的な有機合成反応を開発することを研究目的にしています。
その研究過程で多くの海外,国内の研究者との交流を深めながら研究生活(人生)を楽しみたいと考えています。
External link

Degree

  • Bachelor (Science) ( Hiroshima University )

  • Master (Science) ( Hiroshima University )

  • Doctor (Science) ( The Graduate University for Advanced Studies )

Research Interests

  • functional materials

  • organometallic chemistry

  • トランジスタ

  • 有機太陽電池

  • 機能性材料

  • 有機金属化学

  • transistors

  • organic photovoltaics

Research Areas

  • Nanotechnology/Materials / Polymer chemistry

  • Nanotechnology/Materials / Synthetic organic chemistry

  • Nanotechnology/Materials / Functional solid state chemistry

Education

  • The Graduate University for Advanced Studies   数物科学研究科  

    1994.4 - 1996.8

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    Country: Japan

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  • Hiroshima University   大学院理学研究科   化学専攻

    1992.4 - 1994.3

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    Country: Japan

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  • Hiroshima University   理学部   化学科

    1988.4 - 1992.3

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    Country: Japan

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Research History

  • Okayama University   The Research Institute for Interdisciplinary Science   Professor

    2016.4

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    Country:Japan

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  • Okayama University   The Graduate School of Natural Science and Technology

    2010 - 2016

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  • 岡山大学自然科学研究科機能分子化学専攻 准教授

    2007 - 2010

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  • 岡山大学自然科学研究科機能分子化学専攻 助教授

    2005 - 2007

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  • Okayama University   Faculty of Science

    2004 - 2005

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  • Tokyo Institute of Technology   Chemical Resources Laboratory

    1996 - 2004

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  • 日本学術振興会 特別研究員 日本学術振興会特別研究員

    1996

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Professional Memberships

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Committee Memberships

  • 有機合成化学協会   中国四国支部 監事  

    2020.4   

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    Committee type:Academic society

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  • 有機合成化学協会   代議員  

    2018.4 - 2020.3   

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    Committee type:Academic society

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  • 有機合成化学協会   中国四国支部 幹事  

    2018.4 - 2020.3   

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  • 日本化学会   中国四国支部 代議員  

    2016.4 - 2019.3   

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    Committee type:Academic society

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  • 近畿化学協会有機金属部会   幹事  

    2013.4   

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    Committee type:Academic society

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  • 錯体化学会   「Bulletin of Japan Society of Coordination Chemistry (BJSCC)」 編集委員  

    2012.4 - 2021.9   

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  • 錯体化学会   将来計画委員  

    2011.4 - 2020.3   

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    Committee type:Academic society

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  • 高分子学会   中国四国支部 幹事  

    2010.4   

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    Committee type:Academic society

    高分子学会

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Papers

  • Ni-Catalyzed Decarbonylative Alkynylation of Acyl Fluorides with Terminal Alkynes under Copper-Free Conditions Invited Reviewed

    Qiang Chen, Liyan Fu, Jingwen You, Yasushi Nishihara

    Synlett   32   1560 - 1564   2021.10

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  • Iron-catalysed radical cyclization to synthesize germanium-substituted indolo[2,1-a]isoquinolin-6(5H)-ones and indolin-2-ones Reviewed

    Yani Luo, Tian Tian, Yasushi Nishihara, Leiyang Lv, Zhiping Li

    Chemical Communications   57 ( 73 )   9276 - 9279   2021.8

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  • Formation of trans-Poly(thienylenevinylene) Thin Films by Solid-State Thermal Isomerization Reviewed

    Masayuki Wakioka, Natsumi Yamashita, Hiroki Mori, Richard Murdey, Takafumi Shimoaka, Nobutaka Shioya, Atsushi Wakamiya, Yasushi Nishihara, Takeshi Hasegawa, Fumiyuki Ozawa

    Chemistry of Materials   33 ( 14 )   5631 - 5638   2021.7

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    Cis-to-transisomerization of poly (thienylenevinylene) is found to be a viable fabrication method for semiconducting trans-poly(thienylenevinylene) (trans-P1) thin films. Specifically, thin films of trans-P1, an alternating copolymer containing isoindigo and (E)-1,2-dithienylethene units, which are well known as an excellent p-type semiconductor, were prepared by thermally annealing thin films of the cis-poly(thienylenevinylene) (cis-P1) isomer (92% cis) at 240 degrees C for 30 min. The hole mobility of the isomerized films is comparable to that of films prepared from spin-coated solutions of the trans-isomer. Taking advantage of the greater solubility of the cis-isomer, it was possible to replace the toxic halogenated solvents normally needed for the dissolution of trans-P1 with the environmentally friendly 2-MeTHF. Solid-state cis-to-trans isomerization is therefore a potentially attractive fabrication option for the commercial development of sustainable, printable electronics.

    DOI: 10.1021/acs.chemmater.1c01016

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  • Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C-F Bond Activation Invited Reviewed

    Jingwen You, Qiang Chen, Yasushi Nishihara

    Synthesis   53 ( 17 )   3045 - 3050   2021.4

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:GEORG THIEME VERLAG KG  

    Nickel-catalyzed decarbonylative thioetherification of acyl fluorides has been developed. This transformation allows an array of acyl fluorides to react with thiophenols. A wide range of functional groups are well tolerated and the corresponding sulfides can be obtained in good to excellent yields. This protocol provides the formation of diverse carbon-sulfur bonds via a highly efficient decarbonylative process.

    DOI: 10.1055/a-1484-6216

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  • Recent Advances in Transition-metal-catalyzed C-C Bond Formation via C(sp2)-F Bond Cleavage Reviewed

    Liyan Fu, Qiang Chen, Yasushi Nishihara

    Chemical Records   21   2021.4

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  • Palladium-catalyzed decarbonylative and decarboxylative cross-coupling of acyl chlorides with potassium perfluorobenzoates affording unsymmetrical biaryls Reviewed

    Liyan Fu, Jingwen You, Yasushi Nishihara

    Chemical Communications   57 ( 30 )   3696 - 3699   2021.3

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  • Synthesis and reactivity of boryloxorhodium complexes. Relevance to intermolecular transmetalation from boron to Rhodium in Rh-catalyzed reactions Reviewed

    Yasushi Nishihara, Yasuhiro Nishide, Kohtaro Osakada

    Dalton Transactions   50 ( 10 )   3610 - 3615   2021.2

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    Authorship:Lead author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    <p>The synthesis of a dimeric boryloxorhodium complex having the Rh–O–Bpin scaffold from the reaction of [(cod)Rh(OMe)]2 or [(cod)Rh(OH)]2 with an arylboronate has been achieved. The obtained dirhodium complex is converted...</p>

    DOI: 10.1039/d1dt00440a

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  • Synthesis of 2-Isoxazoline N-Oxides by Copper-Mediated Radical Annulation of Alkenes with α-Nitrobenzyl Bromides Reviewed

    Masayuki Iwasaki, Yuichi Ikemoto, Yasushi Nishihara

    Organic Letters   22 ( 19 )   7577 - 7580   2020.10

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.orglett.0c02781

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  • Synthesis of Oxygen-Containing Heterocyclic Compounds by Iron-Catalyzed Alkylative Cyclization of Unsaturated Carboxylic Acids and Alcohols Reviewed

    Masayuki Iwasaki, Yasuki Kazao, Takumi Ishida, Yasushi Nishihara

    Organic Letters   22 ( 18 )   7343 - 7347   2020.9

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.orglett.0c02671

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  • Efficient Synthesis of π-Conjugated Organic Molecules Utilizing Cross─Coupling Reactions and Application to Electronic Devices Invited Reviewed

    Yasushi Nishihara

    J. Syn. Org. Chem. Jpn.   78 ( 9 )   867 - 874   2020.9

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    Authorship:Lead author, Corresponding author   Language:Japanese   Publishing type:Research paper (scientific journal)  

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  • Synthesis and Physicochemical Properties of 2,7-Disubstituted Phenanthro[2,1-b:7,8-b’]dithiophenes Reviewed

    Zhenfei Ji, Zeliang Cheng, Hiroki Mori, Yasushi Nishihara

    Molecules   25 ( 17 )   3842 - 3842   2020.8

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:MDPI AG  

    We report the design, synthesis, and physicochemical properties of an array of phenanthro[2,1-b:7,8-b’]dithiophene (PDT-2) derivatives by introducing five types of alkyl (CnH2n+1; n = 8, 10, 12, 13, and 14) or two types of decylthienyl groups at 2,7-positions of the PDT-2 core. Systematic investigation revealed that the alkyl length and the type of side chains have a great effect on the physicochemical properties. For alkylated PDT-2, the solubility was gradually decreased as the chain length was increased. For instance, C8-PDT-2 exhibited the highest solubility (5.0 g/L) in chloroform. Additionally, substitution with 5-decylthienyl groups showed poor solubility in both chloroform and toluene, whereas PDT-2 with 4-decylthienyl groups resulted in higher solubility. Furthermore, UV-vis absorption of PDT-2 derivatives substituted by decylthienyl groups showed a redshift, indicating the extension of their π-conjugation length. This work reveals that modification of the conjugated core by alkyl or decylthienyl side chains may be an efficient strategy by which to change the physicochemical properties, which might lead to the development of high-performance organic semiconductors.

    DOI: 10.3390/molecules25173842

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  • Decarboxylative Cross-Coupling of Acyl Fluorides with Potassium Perfluorobenzoates Reviewed

    Liyan Fu, Qiang Chen, Yasushi Nishihara

    Organic Letters   22 ( 16 )   6388 - 6393   2020.8

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    DOI: 10.1021/acs.orglett.0c02215

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  • Syntheses of polynorbornadienes by ring-opening metathesis polymerizations of symmetric and non-symmetric 2,3-bis(alkoxycarbonyl)norbornadienes and their conversion to half-ester derivatives Reviewed

    Jianjun Shi, Yuki Hayashishita, Toshikazu Takata, Yasushi Nishihara, Satomi Niwayama

    Organic & Biomolecular Chemistry   18 ( 34 )   6634 - 6642   2020.7

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    <p>Polymer libraries were synthesized in good yields from half-esters efficiently prepared by the selective monohydrolysis of symmetric diesters we reported.</p>

    DOI: 10.1039/d0ob01252a

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  • Palladium/copper-cocatalyzed decarbonylative alkynylation of acyl fluorides with alkynylsilanes: Synthesis of unsymmetrical diarylethynes Reviewed

    Qiang Chen, Liyan Fu, Yasushi Nishihara

    Chemical Communications   56 ( 57 )   7977 - 7980   2020.6

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  • Methoxylation of Acyl Fluorides with Tris(2,4,6-trimethoxyphenyl)phosphine via C-OMe Bond Cleavage under Metal-Free Conditions Reviewed

    Xiu Wang, Zhenhua Wang, Takumi Ishida, Yasushi Nishihara

    Journal of Organic Chemistry   85 ( 11 )   7526 - 7533   2020.4

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    Acyl fluorides are subjected to methoxylation with tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) to afford the corresponding methyl esters in good to excellent yields. This transformation is featured by C(sp(2))-OMe bond cleavage under metal-free conditions. Unprecedented utilization of TMPP as a methoxylating agent realized the installation of an OMe group into the desired products.

    DOI: 10.1021/acs.joc.0c00640

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  • Synthesis of Dinaphtho[2,3-d:2’,3’-d’]anthra[1,2-b:5,6-b’]dithiophene (DNADT) Derivatives: Effect of Alkyl Chains on Transistor Properties Invited Reviewed

    Takumi Ishida, Yuta Sawanaka, Ryota Toyama, Zhenfei Ji, Hiroki Mori, Yasushi Nishihara

    International Journal of Molecular Sciences   21 ( 7 )   2447 - 2447   2020.4

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    To investigate organic field-effect transistor (OFET) properties, a new thienoacene-type molecule, 4,14-dihexyldinaphtho[2,3-d:2’,3’-d’]anthra[1,2-b:5,6-b’]dithiophene (C6-DNADT), consisting of π-conjugated nine aromatic rings and two hexyl chains along the longitudinal molecular axis has been successfully synthesized by sequential reactions, including Negishi coupling, epoxidation, and cycloaromatization. The fabricated OFET using thin films of C6-DNADT exhibited p-channel FET properties with field-effect mobilities (µ) of up to 2.6 × 10−2 cm2 V−1 s−1, which is ca. three times lower than that of the parent DNADT molecule (8.5 × 10−2 cm2 V−1 s−1). Although this result implies that the installation of relatively short alkyl chains into the DNADT core is not suitable for transistor application, the origins for the FET performance obtained in this work is fully discussed, based on theoretical calculations and solid-state structure of C6-DNADT by grazing incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) analyses. The results obtained in this study disclose the effect of alkyl chains introduced onto the molecule on transistor characteristics.

    DOI: 10.3390/ijms21072447

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  • Palladium-Catalyzed Decarbonylative Alkylation of Acyl Fluorides Reviewed

    Liyan Fu, Qiang Chen, Zhenhua Wang, Yasushi Nishihara

    Organic Letters   22 ( 6 )   2350 - 2353   2020.3

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  • Nickel or Palladium-Catalyzed Decarbonylative Transformations of Carboxylic Acid Derivatives Reviewed

    Zhenhua Wang, Xiu Wang, Yasushi Nishihara

    Chemistry An Asian Journal   15 ( 8 )   1234 - 1247   2020.3

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    Carboxylic acid derivatives containing acyl halides, anhydrides, esters, amides and acyl nitriles are highly appealing electrophiles in transition-metal-catalyzed carbon-carbon bond-forming reactions due to their ready availability and low cost, which can provide divergent transformations of carboxylic acids into other value-added products. In this Minireview, we focus on the recent advances of decarbonylative transformations of carboxylic acid derivatives in carbon-carbon bond formations using Ni or Pd catalysts. A series of reaction types, product classifications and reaction pathways are presented herein, which show the advantageous features of carboxylic acid derivatives as alternative to aryl or alkyl halides in terms of reactivity and compatibility. The well-accepted mechanism of nickel- or palladium-catalyzed decarbonylative transformations involves initial oxidative addition of carboxylic acid derivatives, followed by decarbonylation or transmetalation (or insertion), and reductive elimination to generate the products, thereby regenerating the catalysts.

    DOI: 10.1002/asia.202000117

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  • Copper-Catalyzed Regioselective Aminothiolation of Aromatic and Aliphatic Alkenes with N-Fluorobenzenesulfonimide and Thiols through Three-Component Radical Coupling Reviewed

    Masayuki Iwasaki, Kosei Nonaka, Song Zou, Yuta Sawanaka, Takaaki Shinozaki, Tomoya Fujii, Kiyohiko Nakajima, Yasushi Nishihara

    The Journal of Organic Chemistry   84 ( 23 )   15373 - 15379   2019.12

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.joc.9b02392

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  • Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides Reviewed

    Zhenhua Wang, Xiu Wang, Yasuyuki Ura, Yasushi Nishihara

    Organic Letters   21 ( 17 )   6779 - 6784   2019.9

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    Ni-catalyzed decarbonylative cyanation of acyl chlorides with trimethylsilyl cyanide has been achieved. This transformation is applicable to the synthesis of an array of nitrile compounds bearing a wide range of functional groups under neutral conditions. The step-by-step experimental studies revealed that the reaction sequences of the present catalytic reaction are oxidative addition, transmetalation, decarbonylation, and reductive elimination.

    DOI: 10.1021/acs.orglett.9b02398

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  • Transistor Properties of Semiconducting Polymers Based on Vinylene-bridged Difluorobenzo[c][1,2,5]thiadiazole (FBTzE) Reviewed

    Yuya Asanuma, Hiroki Mori, Yasushi Nishihara

    Chemistry Letters   48 ( 9 )   1029 - 1031   2019.9

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:The Chemical Society of Japan  

    DOI: 10.1246/cl.190304

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  • Nickel/copper-cocatalyzed decarbonylative silylation of acyl fluorides Reviewed

    Wang Xiu, Wang Zhenhua, Nishihara Yasushi

    Chemical Communications   55 ( 71 )   10507 - 10510   2019.8

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    Ni/Cu-cocatalyzed decarbonylative silylation of acyl fluorides with silylboranes has been developed to afford various arylsilanes with high efficiency and good functional-group compatibility via carbon-fluorine bond cleavage and carbon-silicon bond formation. Such transformation can not only extend the functionalization type of acyl fluorides but complement the synthetic route for arylsilanes.

    DOI: 10.1039/c9cc05325e

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  • PPh3-Assisted Esterification of Acyl Fluorides with Ethers via C(sp3)–O Bond Cleavage Accelerated by TBAT Invited Reviewed

    Zhenhua Wang, Xiu Wang, Yasushi Nishihara

    Catalysts   9 ( 7 )   574 - 574   2019.6

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:MDPI AG  

    We describe the (triphenylphosphine (PPh3)-assisted methoxylation of acyl fluorides with cyclopentyl methyl ether (CPME) accelerated by tetrabutylammonium difluorotriphenysilicate (TBAT) via regiospecific C–OMe bond cleavage. Easily available CPME is utilized not only as the solvent, but a methoxylating agent in this transformation. The present method is featured by C–O and C–F bond cleavage under metal-free conditions, good functional-group tolerance, and wide substrate scope. Mechanistic studies revealed that the radical process was not involved.

    DOI: 10.3390/catal9070574

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  • Bis[1]benzothieno[5,4-d:5¤,4¤-d¤]benzo[1,2-b:4,5-b¤]dithiophene Derivatives: Synthesis and effect of sulfur positions on their transistor properties Reviewed

    Shuhei Nishinaga, Masato Mitani, Hiroki Mori, Toshihiro Okamoto, Jun Takeya, Yasushi Nishihara

    Bulletin of the Chemical Society of Japan   92 ( 6 )   1107 - 1116   2019.5

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    © 2019 The Chemical Society of Japan. Bis[1]benzothieno[5,4-d:5¤,4¤-d¤]benzo[1,2-b:4,5-b¤]dithiophene (BBTBDT-2) and its phenyl-substituted derivative were successfully synthesized and characterized. From DFT calculations, highest occupied molecular orbitals (HOMOs) of both compounds are well delocalized and large orbital coefficients exist on sulfur atoms. Single-crystal X-ray analysis revealed that BBTBDT-2 derivatives formed herringbone structures in the solid state. In particular, BBTBDT-2 formed a layer-by-layer structure with effective 2D charge-carrier transporting capability. The fabricated OFETs based on BBTBDT-2 gave mobility up to 0.49 cm2 V11 s11 in the vacuum-deposited thin films, which is the highest value among BBTBDT derivatives including our previously reported syn-counterparts. We have also clarified a detailed structureproperty relationship of sulfur positions and phenyl substituents as indicated by theoretical calculation, GIWAXS, and AFM analyses.

    DOI: 10.1246/bcsj.20180358

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  • Synthesis of 2-Substituted Propenes by Bidentate Phosphine-Assisted Methylenation of Acyl Fluorides and Acyl Chlorides with AlMe3 Reviewed

    Xiu Wang, Zhenhua Wang, Yuya Asanuma, Yasushi Nishihara

    Organic Letters   21 ( 10 )   3640 - 3643   2019.5

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.orglett.9b01059

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  • Nickel-Catalyzed Decarbonylative Stannylation of Acyl Fluorides under Ligand-Free Conditions Invited Reviewed

    Xiu Wang, Zhenhua Wang, Li Liu, Yuya Asanuma, Yasushi Nishihara

    Molecules   24 ( 9 )   1671 - 1671   2019.4

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:MDPI AG  

    Nickel-catalyzed decarbonylative stannylation of acyl fluorides under ligand-free conditions was disclosed. A variety of aromatic acyl fluorides are capable of reacting with silylstannanes in the presence of cesium fluoride. A one-pot decarbonylative stannylation/Migita-Kosugi-Stille reaction of benzoyl fluoride, giving rise to the direct formation of the corresponding cross-coupled products, further demonstrated the synthetic utility of the present method. This newly developed methodology with a good functional-group compatibility via C–F bond cleavage and C–Sn bond formation under nickel catalysis opens a new area for the functionalization of acyl fluorides in terms of carbon-heteroatom bond formation.

    DOI: 10.3390/molecules24091671

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  • Copper-catalyzed Regioselective Chloroamination of Alkenes with Chlorotrimethylsilane and N-Fluorobenzenesulfonimide under Microwave-assisted Conditions Reviewed

    Masayuki Iwasaki, Jie Xu, Yukari Tani, Liyan Fu, Yuichi Ikemoto, Yasuyuki Ura, Yasushi Nishihara

    Chemistry Letters   48 ( 3 )   281 - 284   2019.3

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:The Chemical Society of Japan  

    DOI: 10.1246/cl.180937

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  • Synthesis and Physicochemical Properties of Dibenzo[2,3-d:2′,3′-d′]anthra[1,2-b:5,6-b′]dithiophene (DBADT) and Its Derivatives: Effect of Substituents on Their Molecular Orientation and Transistor Properties Reviewed

    Keita Hyodo, Shuhei Nishinaga, Yuta Sawanaka, Takumi Ishida, Hiroki Mori, Yasushi Nishihara

    The Journal of Organic Chemistry   84 ( 2 )   698 - 709   2019.1

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.joc.8b02557

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  • Vinylene-bridged difluorobenzo[c][1,2,5]-thiadiazole (FBTzE): a new electron-deficient building block for high-performance semiconducting polymers in organic electronics Reviewed

    Yuya Asanuma, Hiroki Mori, Ryosuke Takahashi, Yasushi Nishihara

    Journal of Materials Chemistry C   7 ( 4 )   905 - 916   2019.1

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    <p>A new class of an acceptor unit, vinylene-bridged 5,6-difluorobenzothiadiazole <bold>FBTzE</bold>, and three <bold>FBTzE</bold>-containing copolymers has been synthesized and characterized.</p>

    DOI: 10.1039/c8tc05764h

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  • Nickel-catalysed decarbonylative borylation of aroyl fluorides Reviewed

    Zhenhua Wang, Xiu Wang, Yasushi Nishihara

    Chemical Communications   54 ( 99 )   13969 - 13972   2018.11

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    The first Ni(cod)(2)/PPh3 catalyst system has been established for decarbonylative borylation of aroyl fluorides with bis(pinacolato)diboron. A wide range of functional groups in the substrates were well tolerated. The ease of access of the starting aroyl fluorides indicates that these results might become an alternative to the existing decarbonylation events.

    DOI: 10.1039/c8cc08504h

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  • Development of a phenanthrodithiophene‐difluorobenzoxadiazole copolymer exhibiting high open‐circuit voltage in organic solar cells Reviewed

    Hiroki Mori, Ryosuke Takahashi, Yasushi Nishihara

    Journal of Polymer Science Part A: Polymer Chemistry   56 ( 23 )   2646 - 2655   2018.10

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    DOI: 10.1002/pola.29248

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  • Nickel-Catalyzed Decarbonylative Alkylation of Aroyl Fluorides Assisted by Lewis-Acidic Organoboranes Reviewed

    Yasuhiro Okuda, Jie Xu, Takumi Ishida, Chen-an Wang, Yasushi Nishihara

    ACS OMEGA   3 ( 10 )   13129 - 13140   2018.10

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    Herein, nickel-catalyzed decarbonylative C-F bond alkylation of aroyl fluorides with organoboron reagents is reported. Aroyl fluorides are more chemically stable than the corresponding aroyl chlorides and can be readily synthesized from the corresponding carboxylic acids. The fluoronickel intermediate formed via oxidative addition interacts with Lewis-acidic trialkylboranes, and the subsequent decarbonylative alkylation proceeds. This new synthetic methodology allows 1,2-bifunctionalization of aromatic carboxylic acids via palladium-catalyzed ortho-C-H arylation. addition, an unprecedented 1,4-nickel migration on ortho-atylated aroyl fluorides was observed As a demonstration of the synthetic utility of the present reaction, the sequential 1-alkyl-2-arylation of 3-hydroxy-2-naphthoic acid was accomplished via chemoselective alkylation at a fluorocarbonyl moiety and the subsequent C-O bond arylation at an acetoxy group.

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  • Synthesis and Transistor Characteristics of Dinaphtho[2,3-d:2 ',3 '-d ']anthra[1,2-b:5,6-b ']dithiophene (DNADT) Reviewed

    Nishinaga Shuhei, Sawanaka Yuta, Toyama Ryota, Ishida Takumi, Mori Hiroki, Nishihara Yasushi

    Chemistry Letters   47 ( 11 )   1409 - 1411   2018.9

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  • Regioselective Synthesis of γ‑Lactones by Iron-Catalyzed Radical Annulation of Alkenes with α‑Halocarboxylic Acids and Their Derivatives Reviewed

    Masayuki Iwasaki, Natsumi Miki, Yuichi Ikemoto, Yasuyuki Ura, Yasushi Nishihara

    Org. Lett.   20   3848 - 3852   2018.6

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  • Alkoxy-Substituted Anthra[1,2-c:5,6-c’]bis([1,2,5]-thiadiazole) (ATz): a New Electron-Acceptor Unit in the Semiconducting Polymers for Organic Electronics Reviewed

    Hiroki Mori, Shuhei Nishinaga, Ryosuke Takahashi, Yasushi Nishihara

    Macromolecules   51   5473 - 5484   2018.6

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  • Low-bandgap semiconducting polymers based on sulfur-containing phenacene-type molecules for transistor and solar cell applications Reviewed

    Hiroki Mori, Yasushi Nishihara

    Polymer Journal   50   1 - 11   2018.5

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    The incorporation of a highly extended π-electron system into a polymer backbone is an effective strategy to develop high-performance donor–acceptor (D–A) polymers suitable for organic electronics because this strategy can facilitate a dense π-π stacking structure, leading to efficient carrier transport. With this in mind, we developed phenanthro[1,2-b:8,7-b′]dithiophene (PDT) because this new phenacene-type molecule has a highly crystalline nature, deep HOMO level, and high hole mobility, which are characteristics known to be suitable for a donor unit in high-performance D–A polymers. In this focus review, we report recent progress in PDT-containing D-A polymers combined with various strong acceptor units. Incorporation of PDT into a polymer backbone results in deep HOMO energy levels of −5.4~−5.5 eV, strong aggregation, and a dense packing structure with a short π-stacking distance of 3.5~3.6 Å. PDT-based polymers with appropriate alkyl side chains exhibit high hole mobilities of up to 0.18 cm2 V−1 s−1 in organic field-effect transistor (OFET) devices due to their tendency to form highly ordered edge-on structures. Furthermore, we can adjust their level of molecular orientation from edge-on to face-on by increasing their molecular weight, leading to a high power conversion efficiency of over 6% in polymer solar cell (PSC) applications. These results demonstrate that PDT is a good candidate as a high-performance building block in D-A polymers.

    DOI: 10.1038/s41428-018-0072-4

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  • Efficient Synthesis and Properties of [1]Benzothieno[3,2-b]thieno[2,3-d]furans and [1]Benzothieno[3,2-b]thieno[2,3-d]thiophenes Reviewed

    Yuji Kurimoto, Koichi Mitsudo, Hiroki Mandai, Atsushi Wakamiya, Yasujiro Murata, Hiroki Mori, Yasushi Nishihara, Seiji Suga

    Asian J. Org. Chem.   7   1635 - 1641   2018.5

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  • Effect of Substitution Positions of Alkyl Side Chains in Phenanthrodithiophene–Isoindigo Copolymers: The Enhancement of Crystallinity and Control of Molecular Orders Reviewed

    Hiroki Mori, Shuto Hara, Ryota Toyama, Yuya Asanuma, Ryosuke Takahashi, Shuhei Nishinaga, Yasushi Nishihara

    J. Poly. Sci. Part A: Pol. Chem.   56   1757 - 1767   2018.5

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  • Phenanthrodithiophene (PDT)-Difluorobenzothiadiazole (DFBT) Copolymers: Effect on Molecular Orientation and Solar Cell Performance of Alkyl Substitution onto a PDT Core Reviewed

    Hiroki Mori, Ryosuke Takahashi, Keita Hyodo, Shuhei Nishinaga, Yuta Sawanaka, Yasushi Nishihara

    Macromolecules   51 ( 4 )   1357 - 1369   2018.2

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    Synthesis, characterization, and solar cell application of three 4,7-dialkylated phenanthro[1,2-b:8,7-b′]dithiophene (PDT)-difluorobenzothiadiazole (DFBT copolymers (P1-P3) with different linear alkyl side chains to improve solubility, molecular weight, and molecular orientation are described. The utilization of Ir-catalyzed direct borylation and sequential functionalization can selectively afford the target 4,7-dialkylated PDT as the monomers. Migita-Kosugi-Stille coupling in the presence of CuI can accelerate polymerization to afford high-molecular-weight polymers along with their improved solubility. The effect of alkyl substitution at the 4,7-positions on the electronic structure of PDT-DFBT copolymers is negligible. By installation of additional alkyl chains at the 4,7-positions of PDT, the synthesized polymers P1-P3 have lower intermolecular interaction than that of nonalkylated P0, but they still maintained aggregation behavior in solution. In addition, they formed a favorable face-on orientation with a short π-stacking distance of 3.6 Å, which can enhance their carrier transport ability, resulting in high Jsc and FF. As a result, their fabricated solar cells reached a PCE exceeding 6%, which are about 1.7-fold higher than that of P0. Comparison of alkyl side chain length at the 4,7-positions of PDT revealed that all polymers formed a predominantly face-on orientation and have a similar face-on ratio in blended films, but their crystallinity was decreased as the carbon chains at the 4,7-positions of PDT became shorter. On the other hand, the polymers with short alkyl side chains tended to have low surface roughness and small domain size of active layers, which is an ideal phase separation structure for high-performance PSCs. From these results, it could be seen that the polymers have a trade-off relationship between their domain size and crystallinity, but the impact of alkyl side chain length on their photovoltaic properties is rather small. Thus, the construction of face-on orientation is highly important to achieve a high PCE. Among three polymers, the P3/PC61BM-based solar cell with an optimal nanoscale phase separation structure with bicontinuous domain showed the highest PCE of up to 6.6%.

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  • Synthesis of a 1,2-Dithienylethene-Containing Donor-Acceptor Polymer via Palladium-Catalyzed Direct Arylation Polymerization (DArP) Invited Reviewed

    Masayuki Wakioka, Natsumi Yamashita, Hiroki Mori, Yasushi Nishihara, Fumiyuki Ozawa

    Molecules   23 ( 4 )   981 - 990   2018

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    This paper reports the synthesis of D-A polymers containing 1,2-dithienylethene (DTE) units via palladium-catalyzed direct arylation polymerization (DArP). The reaction of dibromoisoindigo (1-Br) and DTE (2-H), in the presence of Pd2(dba)3·CHCl3 (0.5 mol%), P(2-MeOC6H4)3 (L1) (2 mol%), pivalic acid (1 equiv) as catalyst precursors, and Cs2CO3 (3 equiv) as a base affords poly(1-alt-2) with a high molecular weight (Mn up to 44,900). Although, it has been known that monomers, with plural C–H bonds, tend to form insoluble materials via direct arylation at undesirable C–H positions
    the reaction of 1-Br and 2-H cleanly proceeds without insolubilization. The resulting polymer has a well-controlled structure and exhibits good charge transfer characteristics in an organic field-effect transistor (OFET), compared to the polymer produced by Migita–Kosugi–Stille cross-coupling polymerization. The DArP product displays an ideal linear relationship in the current–voltage curve, whereas the Migita–Kosugi–Stille product shows a VG-dependent change in the charge mobility.

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  • Synthesis and Transistor Application of Bis[1]benzothieno[6,7?d:6',7'?d']benzo[1,2-b:4,5-b']dithiophenes Reviewed

    Shuhei Nishinaga, Hiroki Mori, Yasushi Nishihara

    The Journal of Organic Chemistry   83   5506 - 5515   2018

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  • Direct thiolation and seienation of aryl C-H bonds catalyzed by palladium or nickel Reviewed

    Masayuki Iwasaki, Yasushi Nishihara

    Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry   76 ( 1 )   11 - 20   2018

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    Over the last two decades, transition-metal-catalyzed chelate-assisted direct functionalization of aryl C-H bonds has been well developed. These methodologies realized the efficient carbon -carbon, carbon-oxygen, carbon-nitrogen, and carbon-halogen bond formations. However, the related catalytic direct thiolation and selenation have yet to be disclosed despite the utilities of organosulfur and organoselenium compounds as building blocks in bioactive molecules and functional organic materials. Very recently, several research groups including our group have developed chelate-assisted intermolecular direct thiolation and selenation by using various transition metal catalysts, such as palladium, rhodium, nickel, copper, ruthenium, and cobalt. This article describes our recent studies on chelate-assisted catalytic direct thiolation and selenation of aryl C-H bonds. The reactions with thiols, disulfides, selenols, diselenides, and elemental selenium proceeded well in the presence of palladium or nickel catalyst to provide a variety of organochalcogen compounds. In addition, an appropriate choice of the directing group can be made to control the reaction sites.

    DOI: 10.5059/yukigoseikyokaishi.76.11

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  • Phenanthrene Synthesis by Palladium-Catalyzed Benzannulation with o-Bromobenzyl Alcohols through Multiple Carbon-Carbon Bond Formations Reviewed

    Masayuki Iwasaki, Yasuhiro Araki, Yasushi Nishihara

    JOURNAL OF ORGANIC CHEMISTRY   82 ( 12 )   6242 - 6258   2017.6

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    A palladium-catalyzed benzannulation with o-bromobenzyl alcohols enabled the facile construction of phenanthrene skeletons via the sequential multiple carbon-carbon bond formations. A variety of multisubstituted phenan-threnes were synthesized by the reaction of (Z)-beta-halostyrenes with o-bromobenzyl alcohols as well as by the three-component coupling of alkynes, aryl bromides, and o-bromobenzyl alcohols. The electron-deficient phosphine ligand played an important role to control the sequential oxidative addition of two different organic halides employed, which realized the selective formation of the desired phenanthrenes in good yields. This synthetic protocol was also applicable to the synthesis of the highly fused polycyclic aromatic hydrocarbons such as tetraphenes.

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  • Solar Cell Performance of Phenanthrodithiophene-Isoindigo Copolymers Depends on Their Thin-Film Structure and Molecular Weight Reviewed

    Hiroki Mori, Shuto Hara, Shuhei Nishinaga, Yasushi Nishihara

    MACROMOLECULES   50 ( 12 )   4639 - 4648   2017.6

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    Phenanthro[1,2-b:8,7-b']dithiophene (PDT)isoindigo (IID)-based polymers 12OD (L) and 12OD (H) with a different molecular weight were synthesized and characterized. By using further purified PDT and IID monomers, the high-molecular-weight polymer 12OD (H) with number-average molecular weight (M-n) over 50 kDa was obtained. Both 12OD (L) and 12OD (H) polymers have the same energy gap and highest occupied molecular orbital (HOMO) energy levels, indicating that the influence of molecular weight on their electronic structure is negligible, although 12OD (H) has stronger aggregation behavior than 12OD (L). 12OD (H)-based solar cells fabricated by using optimal solvent and additives showed an increased short-circuit current density (J(sc)) with same open-circuit voltage (V-oc) and fill factor (FF), resulting in a significantly improved power conversion efficiency (PCE) of up to 6.1%, which is approximately 70% higher than that of the 12OD (L)-based cell (3.5%). This result is due to the different molecular orientation caused by the higher molecular weight. Grazing incidence wide-angle X-ray scattering (GIWAXS) analyses revealed that the blended film of 12OD (H)/[6,6]-phenyl-C-61-butyric acid methyl ester (PC61BM) formed a face-on orientation with a long-range ordered structure, while a low crystalline edge-on structure was observed in the blended film of 12OD (L)/PC61BM. Such high crystalline and favorable molecular orientation could promote light harvesting efficiency and hole transporting ability, resulting in high J(sc) and thus an excellent PCE. From the detailed GIWAXS analysis, the orientation change of 12OD (H) was induced by the addition of PC61BM. This result suggests that the strong aggregation ability of 12OD (H) can drive crystallization and favors active interaction with PC61BM to form a face-on orientation. In this study, the increase in molecular weight can improve not only the thin-film structure such as crystallinity and phase separation structure but also the molecular orientation in the PDT-based polymer system.

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  • Synthesis of Benzoisoselenazolone Derivatives by Nickel-Catalyzed Dehydrogenative Direct Selenation of C(sp(2))-H Bonds with Elemental Selenium in Air Reviewed

    Masayuki Iwasaki, Natsumi Miki, Yuta Tsuchiya, Kiyohiko Nakajima, Yasushi Nishihara

    ORGANIC LETTERS   19 ( 5 )   1092 - 1095   2017.3

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    Nickel-catalyzed direct selenation of benzamides bearing an 8-quinolyl auxiliary with elemental selenium provides benzoisoselenazolones in good yield via carbon selenium and nitrogen-selenium bond formation under aerobic conditions. In addition to aryl C-H bonds, the method can also be applied to alkenyl C-H bonds, constructing an isoselenazolone skeleton. Simple mechanistic analysis shows that the reaction proceeds through a rate-determining C-H bond cleavage. The obtained benzoisoselenazolones are transformed into various organoselenium compounds and utilized as the catalyst for bromolactonization of alkenoic acids.

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  • Synthesis and Physicochemical Properties of Piceno[4,3-b:9,10-b′]dithiophene Derivatives and Their Application in Organic Field-Effect Transistors Reviewed

    Keita Hyodo, Ryota Toyama, Hiroki Mori, Yasushi Nishihara

    ACS Omega   2 ( 1 )   308 - 315   2017.1

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    Efficient synthesis and characterization of several piceno[4,3-b:9,10-b′]dithiophene (PiDT) derivatives by Negishi coupling, epoxidation, and Lewis acid-catalyzed cycloaromatization sequences and their potential utility in organic field-effect transistors (OFETs) have been reported. PiDT derivatives, with extended π-electron systems, showed high air stability due to their deep highest occupied molecular orbital energy levels (around -5.6 eV). OFET devices based on 2,11-dioctylated PiDT (C8-PiDT) showed excellent hole mobility, as high as 2.36 cm2 V-1 s-1. Their structure-property relationships were investigated by X-ray diffraction and atomic force microscopy.

    DOI: 10.1021/acsomega.7b00015

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  • Bis[1]benzothieno[2,3-d:2 ',3 '-d ']anthra[1,2-b:5,6-b ']dithiophene: synthesis, characterization, and application to organic field-effect transistors Reviewed

    Keita Hyodo, Hideki Hagiwara, Ryota Toyama, Hiroki Mori, Shin-ichi Soga, Yasushi Nishihara

    RSC ADVANCES   7 ( 10 )   6089 - 6092   2017

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    We report the straightforward synthetic method and characterization of bis[1]benzothieno[2,3-d:2',3'-d']anthra[1,2-b:5,6-b']dithiophene (BBTADT) having nine aromatic rings fused without solubilizing groups. The highest mobility of fabricated OFETs utilizing BBTADT exhibited 2.7 x 10(-2) cm(2) V-1 s(-1) in polycrystalline films formed by vapor deposition, depending on the annealing temperatures of a substrate.

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  • Transistor Properties of 2,7-Dialkyl-Substituted Phenanthro[2,1-b:7,8-b '] dithiophene

    Yoshihiro Kubozono, Keita Hyodo, Shino Hamao, Yuma Shimo, Hiroki Mori, Yasushi Nishihara

    Scientific Reports   6   38535   2016.12

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    A new phenacene-type molecule with five fused aromatic rings was synthesized: 2,7-didodecylphenanthro[2,1-b: 7,8-b'] dithiophene ((C12H25)(2)-i-PDT), with two terminal thiophene rings. Field-effect transistors (FETs) using thin films of this molecule were fabricated using various gate dielectrics, showing p-channel normally-off FET properties with field-effect mobilities (mu) greater than 1cm(2) V-1 s(-1). The highest mu value in the thin-film FETs fabricated in this study was 5.4 cm(2) V-1 s(-1), when a 150 nm-thick ZrO2 gate dielectric was used. This implies that (C12H25)(2)-i-PDT is very suitable for use in a transistor. Its good FET performance is fully discussed, based on electronic/topological properties and theoretical calculations.

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  • Highly Selective Synthesis of Multi-substituted Olefins Mediated by Zirconocene Complexes

    Keita Hyodo, Yasushi Nishihara

    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN   74 ( 8 )   792 - 802   2016.8

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    In this paper, the efficient methodology for the synthesis of multi-substituted olefins by using zirconocene complexes is described. The key step is regioselective formation of zirconacyclopentenes from alkynylboron and alkynylsilane compounds. The subsequent Negishi and Suzuki-Miyaura coupling reactions of C-B and C-Zr bonds give rise to multi-substituted olefins. The developed reaction can be applicable to the synthesis of various functional molecules, for example, an anti-cancer agent. In addition, the mechanism for a regioselective formation of zirconacyclopentenes is analyzed by reactions of alkynylboronates and a zirconocene (II) complex. As a result, it is disclosed that an electrostatic interaction effected the regioselective formation of zirconacyclopentenes. The synthesis of various unprecedented tri- and tetra-alkylated olefins using beta-hydrogen containing alkyl electrophiles and alkylzinc reagents as coupling partners in regio- and stereocontrolled manners is also described.

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  • Synthesis of Multisubstituted Olefins through Regio- and Stereoselective Addition of Interelement Compounds Having B-Si, B-B, and Cl-S Bonds to Alkynes, and Subsequent Cross-Couplings

    Masayuki Iwasaki, Yasushi Nishihara

    CHEMICAL RECORD   16 ( 4 )   2031 - 2045   2016.8

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    Multisubstituted olefins are fundamental motifs in organic compounds. In this account, we describe the synthesis of organic molecules bearing an olefinic moiety by the transition-metal-catalyzed regio- and stereoselective addition of a variety of interelement compounds to alkynes. Regio- and stereoselective silaboration, diborylation, and chlorothiolation have been achieved by using the transition-metal catalysts. The subsequent cross-coupling reactions of the boron-containing alkenes to install various aryl groups afforded the corresponding tri- and tetraarylated olefins. This account describes our research on the highly regio- and stereoselective synthesis of multifunctionalized olefins such as tetraarylethenes with four different aryl groups.

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  • Palladium-Catalyzed Regio- and Stereoselective Carbothiolation of Terminal Alkynes with Azolyl Sulfides

    Masayuki Iwasaki, Nikola Topolovcan, Hao Hu, Yugo Nishimura, Glwadys Gagnot, Rungsaeng Na Nakorn, Ramida Yuvacharaskul, Kiyohiko Nakajima, Yasushi Nishihara

    ORGANIC LETTERS   18 ( 7 )   1642 - 1645   2016.4

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    Palladium-catalyzed carbothiolation of terminal alkynes with azolyl sulfides affords various 2-(azolyl)alkenyl sulfides with perfect regio- and stereoselectivities. The present addition reaction proceeded through a direct cleavage of carbon-sulfur bonds in azolyl sulfides. The resulting adducts that are useful intermediates in organic synthesis are further transformed to multisubstituted olefins containing azolyl moieties.

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  • Highly crystalline, low band-gap semiconducting polymers based on phenanthrodithiophene-benzothiadiazole for solar cells and transistors

    Hiroki Mori, Hikaru Nonobe, Yasushi Nishihara

    POLYMER CHEMISTRY   7 ( 8 )   1549 - 1558   2016

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    New PDT-based polymers were combined with two types of benzothiadiazole (BT) derivatives to improve their crystallinity and solar cell performance. These polymers show several advantages, including strong intermolecular interactions, deep HOMO energy levels, and a dense packing structure with a short pi-pi stacking distance of 3.5-3.6 angstrom. Combinations of PDT and BT units in polymers formed highly crystalline thin films with a long-range order, even in films blended with a fullerene derivative. This suggests that the introduction of optimal acceptor units may increase the regularity of the polymers, leading to effective pi-pi overlaps between the polymer backbones. However, although the present polymers also formed an appropriate phase separation structure in blended films, in fabricated solar cell devices they yielded low power conversion efficiencies (PCEs) not exceeding 3.8%. GI-WAXS analysis revealed that both polymers were present in a predominantly edge-on orientation. This unsuitable orientation for PSCs prevented efficient carrier transport and reduced charge collection efficiency, resulting in low J(sc) and thus low PCE. On the other hand, these polymers also formed highly oriented edge-on structures on n(+)-Si/SiO2 substrates, which are suitable for high-performance field-effect transistors (FETs), and a fabricated FET device showed a hole mobility as high as 0.18 cm(2) V-1 s(-1).

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  • Molecular mechanism of palladium-catalyzed cyanoesterification of methyl cyanoformate onto norbornene Reviewed

    Takuya Ishitsuka, Yasuhiro Okuda, Robert K. Szilagyi, Seiji Mori, Yasushi Nishihara

    Dalton Trans.   45 ( 18 )   7786 - 7793   2016

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    Potential energy surface mapping was completed for the entire catalytic cycle of palladium-catalysed cyanoesterification onto norbornene (NBE) using density functional theory calculations. We found that after the oxidative addition step of the reagent methyl cyanoformate, the reaction proceeds through an insertion of olefin into a Pd-II-COOMe bond first. Subsequently, reductive elimination occurs by transferring the cyanide group from the Pd center to NBE. This rearrangement is triggered by the rotation of the ester group into a pi-interaction with the Pd-II centre. The regioselectivity of olefin insertion is controlled by ionic and covalent interactions in the precursor pi-complex formation step. Importantly, all of the intermediates and transition states along the exo pathway were found to be more stable than the corresponding structures of the endo pathway without any sign of crossing over between the two surfaces via isomerization. The rate-determining step is the reductive elimination despite the fact that the corresponding activation barrier is reduced by conformational changes via the rotation of a MeOOC-C(NBE) bond.

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  • Palladium-catalysed direct thiolation and selenation of aryl C-H bonds assisted by directing groups Reviewed

    Masayuki Iwasaki, Yasushi Nishihara

    DALTON TRANSACTIONS   45 ( 39 )   15278 - 15284   2016

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    Direct chalcogenation of aryl C-H bonds has attracted a lot of attention because arylcharcogen compounds represent useful building blocks in bioactive molecules and functional organic materials. Very recently, chelate-assisted intermolecular direct thiolation and selenation have been developed using various transition-metal catalysts such as palladium, rhodium, nickel, copper and ruthenium. In addition, an appropriate choice of directing group can be used to control the reaction sites. This highlight review focuses on the recent advances in catalytic C-H chalcogenation.

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  • Synthesis of Multisubstituted Triphenylenes and Phenanthrenes by Cascade Reaction of o-lodobiphenyls or (Z)-beta-Halostyrenes with o-Bromobenzyl Alcohols through Two Sequential C-C Bond Formations Catalyzed by a Palladium Complex

    Masayuki Iwasaki, Yasuhiro Araki, Shohei Iino, Yasushi Nishihara

    JOURNAL OF ORGANIC CHEMISTRY   80 ( 18 )   9247 - 9263   2015.9

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    o-Bromobenzyl alcohol has been developed as a novel annulating reagent, bearing both nucleophilic and electrophilic substituents, for the facile synthesis of polycyclic aromatic hydrocarbons. A palladium/electron-deficient phosphine catalyst efficiently coupled o-iodobiphenyls or (Z)-,beta-halostyrenes with o-bromobenzyl alcohols to afford triphenylenes and phenanthrenes, respectively. The present cascade reaction proceeded through deacetonative cross-coupling and sequential intramolecular cyclization. An array of experimental data suggest that the reaction mechanism involves the equilibrium of 1,4-palladium migration.

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  • Impact of Alkyl Side Chains on Thin-film Transistor Performances in Phenanthrodithiophene-Isoindigo Copolymers

    Shuhei Nishinaga, Hiroki Mori, Yasushi Nishihara

    CHEMISTRY LETTERS   44 ( 7 )   998 - 1000   2015.7

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    Organic field-effect transistor (OFET) characteristics of phenanthrodithiophene (PDT)-isoindigo (IID) copolymers with different alkyl chains (12OD and BOBO) as an active layer, and their structure property relationships are described. The fabricated 12OD-based OFET device exhibited hole mobility of 0.16 cm(2)V(-1) s(-1). Grazing-incidence wide-angle X-ray scattering (GIWAXS) analysis revealed that 12OD formed highly ordered edge-on structure, whereas the BOBO film showed amorphous-like structure with no obvious pi-stacking crystallites. This may be attributed to a large steric hindrance of branched side chains in the BOBO polymer, which suppresses effective pi-pi overlaps between the adjacent polymer backbones.

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  • Phenanthrodithiophene-Isoindigo Copolymers: Effect of Side Chains on Their Molecular Order and Solar Cell Performance

    Shuhei Nishinaga, Hiroki Mori, Yasushi Nishihara

    MACROMOLECULES   48 ( 9 )   2875 - 2885   2015.5

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    The synthesis;,characterization, and solar cell application of newly developed semiconducting polymers containing phenanthro[1,2-b:8,7-b']dithiophene (PDT) combined with A bis(thienyl)isoindigo (IID) unit are,described. The polymers with longer, alkyl Chains are sufficiently soluble to be compatible with the processes required to manufacture solar cells. In conventional solar cell, devices, polymers with all branched alkyl chains tend to form a higher proportion of a well-ordered face-on crystallite in the pi-stack direction than those with both linear and branched alkyl chains, which significantly improves the Ell factor (FF), resulting in higher power conversion efficiency (PCE). In terms of optimizing the alkyl chain lengths; the installation of longer alkyl side chains on the polymer backbone leads to low molecular weight polymer, which may promote a large phase separation. As a result, the polymers 12OD and BOBO, beating shorter alkyl groups, performed better, and a BOBO polymer-based solar cell (PSC) showed the best PCE value up to 3.83%. In the inverted PSCs, the polymers with all branched alkyl chains have a higher face-on ratio than those with both linear and branched alkyl chains. Because of their improved J(sc), inverted PSCs with BOBO/PC71BM gave the best performance, with a PCE up to 5.28%. Although an obvious dependence of photovoltaic properties on molecular order-was observed in conventional solar cell devices, no trend was observed in inverted cells, Possibly attributable to their amorphous nature, which arises from the axisymmetrical structure of PDT, leading to less effective pi-pi overlap and low crystallinity.

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  • Erratum: Transistor application of new picene-type molecules, 2,9-dialkylated phenanthro[1,2-b:8,7-b′]dithiophenes (Journal of Materials Chemistry C (2015) 3 DOI: 10.1039/c4tc02413c) Reviewed

    Yoshihiro Kubozono, Keita Hyodo, Hiroki Mori, Shino Hamao, Hidenori Goto, Yasushi Nishihara

    Journal of Materials Chemistry C   3 ( 12 )   2960   2015.3

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    DOI: 10.1039/c5tc90044a

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  • Synthesis, Characterization, and Solar Cell and Transistor Applications of Phenanthro[1,2-b:8,7-b ']dithiophene-Diketopyrrolopyrrole Semiconducting Polymers

    Hiroki Mori, Masato Suetsugu, Shuhei Nishinaga, Ning-hui Chang, Hikaru Nonobe, Yasuhiro Okuda, Yasushi Nishihara

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   53 ( 5 )   709 - 718   2015.3

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    Synthesis, characterization, and polymer solar cell and transistor application of a series of phenanthro[1,2-b:8,7-b]dithiophene-based donor-acceptor (D-A)-type semiconducting polymers combined with a diketopyrrolopyrrole unit are reported. The present polymers showed some unique features such as strong aggregation behavior, high thermal stability, and short - stacking distance (3.5-3.6 angstrom), which are suitable for high performance organic materials. In addition, they have a significantly extended absorption up to 1000 nm with a band gap of ca. 1.2 eV. However, such strong intermolecular interaction reduced their solubility and molecular weights, which resulted in low crystalline nature and moderate field-effect mobility of 0.01 cm(2) V-1 s(-1). Furthermore, such strong aggregation behavior led to the large-scale phase separation in the blend films, which may prevent the effective photocurrent generation, limiting J(sc) and power conversion efficiency of 2.0%. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 709-718

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  • Transistor application of new picene-type molecules, 2,9-dialkylated phenanthro[1,2-b:8,7-b ']dithiophenes

    Yoshihiro Kubozono, Keita Hyodo, Hiroki Mori, Shino Hamao, Hidenori Goto, Yasushi Nishihara

    JOURNAL OF MATERIALS CHEMISTRY C   3 ( 10 )   2413 - 2421   2015

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    Field-effect transistors (FETs) have been fabricated with thin films of a series of 2,9-dialkylated phenanthro [1,2-b:8,7-b'] dithiophene derivatives (C-n-PDTs). The FET characteristics of C-n-PDT thin-film FETs with an SiO2 gate dielectric as well as high-k gate dielectrics were recorded, and the dependence of the field-effect mobility, mu, on the number (n) of carbon atoms in the alkyl chains was investigated, showing that the 2,9-didodecylphenanthro[1,2-b:8,7-b'] dithiophene (C-12-PDT) thin-film FET displays superior properties, with mu s as high as 1.8 cm(2) V-1 s(-1) for the SiO2 gate dielectric and 2.2 cm(2) V-1 s(-1) for the HfO2 gate dielectric. The average mu values, &lt;mu &gt;, reach 1.1(5) and 1.8(6) cm(2) V-1 s(-1), respectively, for the SiO2 and ZrO2 gate dielectrics. Low-voltage operation, showing an absolute average threshold voltage &lt;|V-th|&gt; of similar to 11 V, was implemented, together with the above high &lt;mu &gt; of similar to 2 cm(2) V-1 s(-1). Also, a flexible FET was fabricated with a parylene gate dielectric. The results of this study show the potential of the C-12-PDT molecule for application in a high-performance transistor.

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  • A divergent synthesis of 3,10-dialkylpicenes

    Xi-Chao Chen, Shuhei Nishinaga, Yasuhiro Okuda, Jia-Ji Zhao, Jie Xu, Hiroki Mori, Yasushi Nishihara

    Organic Chemistry Frontiers   2 ( 5 )   536 - 541   2015

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    A series of 3,10-dialkylated picenes has been synthesized from 3,10-dimethoxypicene through a divergent approach involving Ni-catalyzed alkynylation of a C-O bond, alkylation, and hydrogenation.

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  • Palladium-Catalyzed pen-Selective Chalcogenation of Naphthylamines with Diaryl Disulfides and Diselenides via C-H Bond Cleavage

    Masayuki Iwasaki, Wataru Kaneshika, Yuta Tsuchiya, Kiyohiko Nakajima, Yasushi Nishihara

    JOURNAL OF ORGANIC CHEMISTRY   79 ( 23 )   11330 - 11338   2014.12

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    A palladium-catalyzed and picolinamide-directed C-H thiolation of naphthylamine derivatives with diaryl disulfides has been developed to provide a convenient route to 8-sulfenyl-1-naphthylamines. The reaction proceeds via a 5-membered palladacycle intermediates to afford the peri-thiolated products exclusively, in contrast to the conventional ortho-functionalization. Moreover, the related direct selenation was also achieved with diaryl diselenides, giving the corresponding selenated products with perfect site-selectivity.

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  • Iron-Induced Regio- and Stereoselective Addition of Sulfenyl Chlorides to Alkynes by a Radical Pathway Reviewed

    Masayuki Iwasaki, Tomoya Fujii, Kiyohiko Nakajima, Yasushi Nishihara

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   53 ( 50 )   13880 - 13884   2014.12

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    The radical addition of the ClS sigma-bond in sulfenyl chlorides to various CC triple bonds has been achieved with excellent regio- and stereoselectivity in the presence of a catalytic amount of a common iron salt. The reaction is compatible with a variety of functional groups and can be scaled up to the gram-scale with no loss in yield. As well as terminal alkynes, internal alkynes underwent stereodefined chlorothiolation to provide tetrasubstituted alkynes. Preliminary mechanistic investigations revealed a plausible radical process involving a sulfur-centered radical intermediate via iron-mediated homolysis of the ClS bond. The resulting chlorothiolation adducts can be readily transformed to the structurally complex alkenyl sulfides by cross-coupling reactions. The present reaction can also be applied to the complementary synthesis of the potentially useful bis-sulfoxide ligands for transition-metal-catalyzed reactions.

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  • Chelate-Assisted Direct Selenation of Aryl C-H Bonds with Diselenides Catalyzed by Palladium Reviewed

    Masayuki Iwasaki, Yuta Tsuchiya, Kiyohiko Nakajima, Yasushi Nishihara

    ORGANIC LETTERS   16 ( 18 )   4920 - 4923   2014.9

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    A direct selenation of inert C-H bonds of benzamide derivatives and their related compounds with diselenides has been achieved with the palladium catalyst. The reaction was compatible with a variety of functional groups, including a bromo group. Primitive mechanistic insights revealed that the reaction proceeded through a C H bond cleavage and the sequential oxidative addition of diselenides. The present synthetic method can be applied to the facile synthesis of selenoxanthone which can be regarded as promising heterocyclic materials.

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  • Transistor Application of Phenacene Molecules and Their Characteristics

    Yoshihiro Kubozono, Xuexia He, Shino Hamao, Kazuya Teranishi, Hidenori Goto, Ritsuko Eguchi, Takashi Kambe, Shin Gohda, Yasushi Nishihara

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY   2014 ( 24 )   3806 - 3819   2014.8

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    The characteristics of field-effect transistors (FETs) fabricated from thin films and single crystals of phenacene molecules are fully reported in this review together with the electronic and crystal structures of phenacenes. Phenacene molecules possess a low HOMO level and a wide band gap. The highest mobility observed in the phenacene thin-film FETs is 7.4 cm(2)V(-1)s(-1) for [6]phenacene, and in single-crystal FETs the highest value is 6.3 cm(2)V(-1)s(-1) for [7]phenacene. The phenacene thin-film FETs show O-2-sensing properties unlike their single-crystal FETs. The bias-stress effect is fully investigated for phenacene single-crystal FETs. Furthermore, the low-voltage operation of phenacene single-crystal FETs with electric-double-layer (EDL) capacitors is reported. The temperature dependence of phenacene single-crystal FETs is reported to clarify the transport mechanism, which is suggestive of band-like transport.

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  • New Entry to the Synthesis of alpha-Iminonitriles by Lewis Acid Mediated Isomerization of Cyano-Substituted Iminoisobenzofurans Prepared by Palladium-Catalyzed Three-Component Coupling of Arynes, Isocyanides, and Cyanoformates

    Jing Li, Shintaro Noyori, Kiyohiko Nakajima, Yasushi Nishihara

    ORGANOMETALLICS   33 ( 13 )   3500 - 3507   2014.7

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    A variety of alpha-iminonitriles were formed as the minor products of three-component coupling reactions of arynes, isocyanides, and cyanoformates in the presence of the cationic palladium complex [Pd(NCPh)(2)(dppf)1(BF4)(2) as the catalyst, along with cyano-substituted iminoisobenzofurans as the major products. alpha-Iminonitriles obtained from this process are hardly accessible by conventional methods. In addition, when the isolated iminoisobenzofurans were treated with diisobutylaluminum hydride (DIBAL-H) or AlMe3, the transformation of cyano-substituted iminoisobenzofurans into alpha-iminonitriles was observed.

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  • Synthesis of 2,9-dialkylated phenanthro[1,2-b:8,7-b ']dithiophenes via cross-coupling reactions and sequential Lewis acid-catalyzed regioselective cycloaromatization of epoxide Reviewed

    Keita Hyodo, Hikaru Nonobe, Shuhei Nishinaga, Yasushi Nishihara

    TETRAHEDRON LETTERS   55 ( 29 )   4002 - 4005   2014.7

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    Phenanthro[1,2-b:8,7-b']dithiophene (PDT) was prepared via Suzuki-Miyaura or Negishi cross-coupling of a 2-thienylboron or -zinc compound with 1,4-dibromobenzene, followed by Lewis acid-catalyzed regioselective cycloaromatization of the epoxide. A series of 2,9-dialkylated phenanthro[1,2-b:8,7-b']dithiophene (PDT) derivatives could also be synthesized in good yields by Suzuki-Miyaura coupling of the brominated PDT with alkylboranes by introducing linear alkyl substituents. (C) 2014 Elsevier Ltd. All rights reserved.

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  • Synthesis of Methoxy-Substituted Picenes: Substitution Position Effect on Their Electronic and Single-Crystal Structures

    Hiroki Mori, Xi-chao Chen, Ning-hui Chang, Shino Hamao, Yoshihiro Kubozono, Kiyohiko Nakajima, Yasushi Nishihara

    JOURNAL OF ORGANIC CHEMISTRY   79 ( 11 )   4973 - 4983   2014.6

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    A series of picenes having methoxy groups was synthesized through Pd-catalyzed Suzuki-Miyaura couplings or Wittig reaction/intramolecular cyclization sequences, and their physicochemical properties and single-crystal structures were evaluated. The substitution position effects between the outer 1,12-, 2,11-, and 4,9-position and the inner 3,10-position are quite different; the former showed the same electronic structure as that of picene, but the latter results in a HOMO geometry different from those of picene and other methoxy picenes. In addition, crystal structures of four types of methoxy-substituted picenes 4a-c,e strongly depend on their substitution position and number of methoxy groups, which dramatically changes the structures from the fully anisotropic 1D pi-stacked structure to a unique 3D herringbone structure due to steric hindrance of methoxy groups. The calculations of transfer integrals based on their single-crystal structures reveal that the methoxy picenes have intermolecular overlaps less effective than that of the parent nonsubstituted picene. These results are attributed not only to the packing structure but also to electronic structures such as the HOMO distribution. The preliminary OFET of the representative 4c,e showed hole mobilities significantly lower than that of picene due to their less effective intermolecular overlaps, as predicted by the calculated transfer integrals.

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  • Palladium- Catalyzed Direct Thiolation of Aryl C similar to H Bonds with Disulfides Reviewed

    Masayuki Iwasaki, Miki Iyanaga, Yuta Tsuchiya, Yugo Nishimura, Wenjuan Li, Zhiping Li, Yasushi Nishihara

    CHEMISTRY-A EUROPEAN JOURNAL   20 ( 9 )   2459 - 2462   2014.2

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    A catalytic variant of the direct thiolation of arenes, bearing directing groups, with disulfides or thiols has been developed under palladium and copper co-catalysis. Both sulfenyl moieties of the disulfide could be incorporated into the thiolated products, therefore, the reactions reached completion with only half an equivalent of disulfide, with respect to the starting arene. Experimental evidence suggested that the reaction proceeds through a Pd-II/Pd-IV mechanism.

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  • Palladium-Catalyzed Regio- and Stereoselective Chlorothiolation of Terminal Alkynes with Sulfenyl Chlorides Reviewed

    Masayuki Iwasaki, Tomoya Fujii, Arisa Yamamoto, Kiyohiko Nakajima, Yasushi Nishihara

    CHEMISTRY-AN ASIAN JOURNAL   9 ( 1 )   58 - 62   2014.1

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    Chlorothiolation of terminal alkynes with sulfenyl chlorides yields anti-adducts without transition-metal catalysts. In sharp contrast, transition-metal-catalyzed chlorothiolation has not been developed to date, possibly because organosulfur compounds can poison catalyst. Herein, the regio- and stereoselective palladium-catalyzed chlorothiolation of terminal alkynes with sulfenyl chlorides is described. syn-Chlorothiolation offers a complementary synthetic route to chloroalkenyl sulfides. 2-Chloroalkenyl sulfides can easily be transformed into various sulfur-containing products, most of which are often found in natural products and pharmaceuticals.

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  • Selective Synthesis of Multisubstituted Olefins Utilizing gem- and vic-Diborylated Vinylsilanes Prepared by Silylborylation of an Alkynylboronate and Diborylation of Alkynylsilanes Reviewed

    Jiao Jiao, Keita Hyodo, Hao Hu, Kiyohiko Nakajima, Yasushi Nishihara

    JOURNAL OF ORGANIC CHEMISTRY   79 ( 1 )   285 - 295   2014.1

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    The synthesis of a series of gem- and vic-diborylated vinylsilanes was accomplished via highly selective transition-metal-catalyzed syn-dimetalation to the alkynylmetal species. This protocol served as a general synthetic method toward regio- and stereodefined multisubstituted olefins. The key steps are the diastereoselective Suzuki-Miyaura cross-coupling reactions of gem- and vic-diborylated vinylsilanes, in which the two boron groups showed discrete reactivities to afford diverse precursors of multisubstituted olefins.

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  • Diborylation of Alkynyl MIDA Boronates and Sequential Chemoselective Suzuki-Miyaura Couplings: A Formal Carboborylation of Alkynes Reviewed

    Keita Hyodo, Masato Suetsugu, Yasushi Nishihara

    ORGANIC LETTERS   16 ( 2 )   440 - 443   2014.1

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    Platinum-catalyzed diborylation of phenylethynyl MIDA boronate with B-pin-B-pin proceeds to yield 1,1,2-triboryl-2-phenylethene with two different classes of the boron functionalities. Sequentially, the obtained 1,1,2-triboryl-2-phenylethene are subjected to Suzuki-Miyaura coupling to introduce a series of aryl groups chemoselectively to afford 1,1-boryl-2,2-diarylethenes.

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  • Phenanthro[1,2-b:8,7-b']dithiophene: A new picene-type molecule for rransistor applications Reviewed

    Yasushi Nishihara, Megumi Kinoshita, Keita Hyodo, Yasuhiro Okuda, Ritsuko Eguchi, Hidenori Goto, Shino Hamao, Yasuhiro Takabayashi, Yoshihiro Kubozono

    RSC Advances   3 ( 42 )   19341 - 19347   2014

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    A new picene-type molecule, phenanthro[1,2-b : 8,7-b'] dithiophene, has been synthesized for use in organic field-effect transistors (OFETs). The molecule consists of a phenanthrene core with two thiophene rings fused on the ends. This molecule can be recognized as a picene analogue. The electronic structure of the molecule was determined by its optical absorption spectrum together with a theoretical calculation based on density functional theory (DFT). The topological and electronic structures of thin films produced by direct thermal evaporation of the compounds and by deposition from a solution were characterized by optical imaging, X-ray diffraction, and atomic force microscopy. FET devices were fabricated with these thin films, and showed field-effect mobility as high as 10(-1) cm(2) V-1 s(-1).

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  • Synthesis, structure, and isomerization of alkoxycarbonyl(chloro)(cyano)rhodium(III) complexes, mer- RhCl(CO2R)(CN)(PMe3)3 (R = Me, Et, nPr, iPr, nBu, and Bn) through C–C bond cleavage of cyanoformates Reviewed

    Yasuhiro Okuda, Takeru Okamoto, Arisa Yamamoto, Jing Li, Kiyohiko Nakajima, Yasushi Nishihara

    Chem. Lett.   43 ( 4 )   417 - 419   2014

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    Alkoxycarbonyl(chloro)(cyano)rhodium(III) complexes mer-[RhCl(CO2R)(CN)(PMe3)(3)] (1: R = Me; 2: R = Et; 3: R = Pr-n; 4: R = Pr-i; 5: R = Bu-n; 6: R = Bn) are prepared via oxidative addition of the corresponding cyanoformates to [RhCl(PMe3)(3)], derived in situ from [RhCl(cod)](2) and three equivalents of PMe3 in toluene at 70 degrees C, and their structures are characterized using NMR (H-1, C-13{H-1}, and P-31{H-1)) and X-ray diffraction.

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  • Experimental and Theoretical Studies on the Platinum-Mediated Selective C(sp)-Si Bond Cleavage of Alkynylsilanes Reviewed

    Yasuhiro Okuda, Yuya Ishiguro, Seiji Mori, Kiyohiko Nakajima, Yasushi Nishihara

    Organometallics   33 ( 7 )   1878 - 1889   2014

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    A series of cis-alkynyl(silyl)platinum(II) complexes was prepared via the chemoselective C(sp)-Si bond cleavage of alkynylsilanes by a platinum(0) complex ligated with the P-N hemilabile bidentate ligand. The coordination of the triple bond to the platinum center triggers selective C(sp) Si bond cleavage. Hammett plots of the P-31{H-1} NMR spectroscopic properties (delta and J values) reflect an electronic effect on platinum(II) complexes; trans substituents of arylethynyl groups are influenced, but cis-positioned silyl groups are not affected, as evidenced by Si-29{H-1} NMR. In comparison, Hammett plots show that C(sp) Si bond cleavage rates are accelerated by electron-rich alkynylsilanes, which is opposite to the ordinary oxidative addition of aryl halides to transition metals often observed in catalytic cross-coupling reactions. A DFT calculation reveals that intermediates and transition states are stabilized by electron-rich alkynylsilanes and that the five-membered hemilabile P-N ligand is essential, in which a reactive electron-deficient 14-electron platinum(0) species is produced via the dissociation of nitrogen, giving rise to a monodentate phosphine coordination. Electron-rich alkynylsilanes allow decreased pi back-donation from the platinum center to the ligand, accelerating the dissociation of the more labile nitrogen. Steric congestion between diisopropylphosphino and silyl groups thermodynamically disfavors C(sp)-Si bond cleavage.

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  • Skeletal rearrangement of cyano-substituted iminoisobenzofurans into alkyl 2-cyanobenzoates catalyzed by B(C6F5)3 Reviewed

    Jing Li, Yasuhiro Okuda, Jiaji Zhao, Seiji Mori, Yasushi Nishihara

    Org. Lett.   16 ( 19 )   5220 - 5223   2014

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    An efficient method for the direct conversion of cyano-substituted iminoisobenzofurans into their corresponding alkyl 2-cyanobenzoates has been developed. This transformation proceeds via cleavage of C-C, C-O, and C-N bonds in starting iminoisobenzofurans. DFT study revealed that intermediate a-iminonitriles are produced in situ via C-C bond formation between 2-iminium benzoates and a cyanide ion. Generation of isocyanide as the byproduct in a more thermodynamic manner in DFT calculations also supports the experimental results.

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  • The origin of exo-selectivity in methyl cyanoformate addition onto the C=C bond of norbornene in Pd-catalyzed cyanoesterification” Reviewed

    Yasuhiro Okuda, Robert Szilagyi, Seiji Mori, Yasushi Nishihara

    Dalton Trans.   43 ( 25 )   9537 - 9548   2014

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    A computational investigation has been carried out to elucidate the origin of the exclusive exo-selectivity in the Pd-catalyzed cyanoesterification of strained cyclic olefins, norbornene and norbornadiene. A hybrid density functional was selected for the level of theory with a triple-zeta quality basis set, which was proposed in an earlier study to provide an experimentally sound ground state electronic structure description for palladium(II) and palladium(IV) complexes from multi-edge X-ray absorption spectroscopic measurements. Given that the product of oxidative addition can be isolated, we focused on the olefin coordination as the earliest possible origin of exo-selectivity. The calculated geometric structure for the trans-Pd(CN)(COOR)(PPh3)(2) complex at the BHandHLYP/ def2TZVP/ PCM(toluene) level is in an excellent agreement with its experimental structure from crystallographic measurements. Upon dissociation of one of its phosphane ligands, the coordinatively unsaturated trans-isomer is only 17 kJ mol(-1) away from the isomerization transition state, leading to the 14-electron cis-isomers that are 17 to 37 kJ mol(-1) lower in energy than the trans-isomers. Regardless of the initial complex for olefin coordination, the exo-isomer for the norbornene complex is at least 8 kJ mol(-1) lower than the corresponding endo-isomer. The origin of this considerable difference in Gibbs free energy can be attributed to the remarkably different steric and agostic hydrogen interactions between the methylene and the ethylene bridges of the norbornene and the adjacent cis-ligands at the Pd-II center.

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  • Palladium-Catalyzed Annulation of o-lodobiphenyls with o-Bromobenzyl Alcohols: Synthesis of Functionalized Triphenylenes via C-C and C-H Bond Cleavages Reviewed

    Masayuki Iwasaki, Shohel Lino, Yasushi Nishihara

    ORGANIC LETTERS   15 ( 20 )   5326 - 5329   2013.10

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    Treatment of o-iodobiphenyls with abromobenzyl alcohols in the presence of cesium carbonate under palladium catalysis affords a series of highly substituted triphenylenes. The reaction involves two C-C bond formations and C-C and C-H bond cleavages. A combination of palladium and an electron-deficient phosphine ligand proves to be effective for both decarbonylative cross-coupling and intramolecular cyclization.

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  • Synthesis of Multisubstituted Olefins through Regio- and Stereoselective Silylborylation of an Alkynylboronate/Chemoselective Cross-Coupling Sequences Reviewed

    Jiao Jiao, Kiyohiko Nakajima, Yasushi Nishihara

    ORGANIC LETTERS   15 ( 13 )   3294 - 3297   2013.7

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    A highly regio- and stereoselective silylborylation of an alkynylboronate is disclosed. PhMe2Si-B-pin undergoes a Pd(OAc)(2)/(t)OctNC-catalyzed syn-addition to the alkynylboronate to yield 1-phenyl-1-silyl-2,2-diborylethene with high regioselectivity. The product 1-phenyl-1-silyl-2,2-diborylethene is then chemoselectively arylated by Suzuki-Miyaura coupling to afford (2)-1-silyl-2-borylstilbene derivatives. This approach is extended to the synthesis of a tetraarylated olefin with four different substituents.

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  • Synthesis of cyclic 1-alkenylboronates via Zr-mediated double functionalization of alkynylboronates and sequential Ru-catalyzed ring-closing olefin metathesis Reviewed

    Yasushi Nishihara, Masato Suetsugu, Daisuke Saito, Megumi Kinoshita, Masayuki Iwasaki

    Organic Letters   15 ( 10 )   2418 - 2421   2013.5

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    Synthesis of novel cyclic 1-alkenylboronates is accomplished through the zirconium-mediated regio- and stereoselective double functionalization of 1-alkynylboronates and the subsequent ruthenium-catalyzed ring-closing metathesis (RCM). The obtained substituted cyclic 1-alkenylboronates are transformed into o-terphenyl and triphenylene derivatives. © 2013 American Chemical Society.

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  • Palladium-catalyzed and copper-mediated cross-coupling reaction of aryl- or alkenylboronic acids with acid chlorides under neutral conditions: efficient synthetic methods for diaryl ketones and chalcones at room temperature Reviewed

    Daisuke Ogawa, Keita Hyodo, Masato Suetsugu, Jing Li, Yoshiaki Inoue, Mamoru Fujisawa, Masayuki Iwasaki, Kentaro Takagi, Yasushi Nishihara

    TETRAHEDRON   69 ( 12 )   2565 - 2571   2013.3

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    Palladium-catalyzed cross-coupling reaction of aryl- or alkenylboronic acids with acid chlorides in the presence of copper(I) thiophene-2-carboxylate (CuTC) as an activator in diethyl ether at room temperature under strictly non-basic conditions affords the diaryl ketones or chalcones in moderate to excellent yields. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on the aromatic ring are compatible. (C) 2013 Elsevier Ltd. All rights reserved.

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  • Palladium-free synthesis of unsymmetrical diarylethynes by cross-coupling reaction of alkynylboronates with aryl iodides catalyzed by CuCl Reviewed

    Daisuke Ogawa, Jing Li, Masato Suetsugu, Jiao Jiao, Masayuki Iwasaki, Yasushi Nishihara

    TETRAHEDRON LETTERS   54 ( 6 )   518 - 521   2013.2

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    A series of unsymmetrical diarylethynes have been synthesized by the copper-catalyzed cross-coupling reaction of alkynylboronates with aryl iodides in high to excellent yields under palladium-free conditions. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on the aromatic ring are compatible with this reaction. (C) 2012 Elsevier Ltd. All rights reserved.

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  • Synthesis of substituted [6]phenacenes through Suzuki–Miyaura coupling of polyhalobenzene with alkenylboronates and sequential intramolecular cyclization via C–H bond activation Reviewed

    Ning-hui Chang, Hiroki Mori, Xi-chao Chen, Yasuhiro Okuda, Takeru Okamoto, Yasushi Nishihara

    Chem. Lett.   42 ( 10 )   1257 - 1259   2013

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    A series of substituted [6]phenacenes were synthesized through the Suzuki-Miyaura coupling and intramolecular double cyclization, using a polyhalobenzene and two different alkenylboronates. This methodology provides a direct route to unsymmetrical [6]phenacenes. The physicochemical properties of four [6]phenacenes were evaluated using UV-vis and fluorescence spectroscopies as well as cyclic voltammetry.

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  • Synthesis of Substituted Picenes through Pd-Catalyzed Cross-Coupling Reaction/Annulation Sequences and Their Physicochemical Properties Reviewed

    Ning-hui Chang, Xi-chao Chen, Hikaru Nonobe, Yasuhiro Okuda, Hiroki Mori, Kiyohiko Nakajima, Yasushi Nishihara

    Org. Lett.   15 ( 14 )   3558 - 3561   2013

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    A novel and versatile synthetic method for picene derivatives is developed using the Pd-catalyzed intramolecular double cyclization of the corresponding 2,3-bis[(1Z)-2-phenylethenyl]-1,4-dichlorobenzenes, which are readily prepared by Suzuki-Miyaura cross-coupling reactions of polyhalobenzenes with (Z)-arylethenylboronates. The physical properties of the obtained picenes can be modified via introducing a variety of functional groups to the picene frame-work All compounds are investigated by UV-vis and fluorescence spectroscopic measurements, CV, and DFT calculations as well as X-ray diffraction analysis.

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  • A NOVEL THREE-COMPONENT COUPLING REACTION OF ARYNES, ISOCYANIDES, AND CYANOFORMATES: A STRAIGHTFORWARD ACCESS TO CYANO-SUBSTITUTED IMINOISOBENZOFURANS Reviewed

    Jing Li, Shintaro Noyori, Masayuki Iwasaki, Kiyohiko Nakajima, Yasushi Nishihara

    HETEROCYCLES   86 ( 2 )   933 - 940   2012.12

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    Iminoisobenzofuran derivatives have been prepared in moderate yields by the palladium-catalyzed three-component coupling reaction of arynes, isocyanides, and cyanoformates. This paper is dedicated to Professor Ei-ichi Negishi on the occasion of his 77th birthday.

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  • Synthesis of Unsymmetrical Diarylethynes by Pd(0)/Cu(I)-cocatalyzed Sila-Sonogashira-Hagihara Coupling Reactions of Alkynylsilanes with Aryl Tosylates or Mesylates Reviewed

    Yasushi Nishihara, Daisuke Ogawa, Shintaro Noyori, Masayuki Iwasaki

    CHEMISTRY LETTERS   41 ( 11 )   1503 - 1505   2012.11

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    Palladium/copper-cocatalyzed cross-coupling reactions of alkynylsilanes with aryl tosylates or mesylates afforded the corresponding unsymmetrical diarylethynes in moderate to good yields. The optimized reaction conditions to afford higher yields of cross-coupled products were found to be 5 mol % of [PdCl2(bpy)], 15 mol % of BrettPhos, and 10 mol % of (CuCl)-Cl-I in DMF as a solvent.

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  • Synthesis of unsymmetrically disubstituted ethynes by the palladium/copper(I)-cocatalyzed sila-Sonogashira-Hagihara coupling reactions of alkynylsilanes with aryl iodides, bromides, and chlorides through a direct activation of a carbon-silicon bond Reviewed

    Yasushi Nishihara, Eiji Inoue, Shintaro Noyori, Daisuke Ogawa, Yoshiaki Okada, Masayuki Iwasaki, Kentaro Takagi

    TETRAHEDRON   68 ( 24 )   4869 - 4881   2012.6

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    In this paper, we explore the copper/palladium-cocatalyzed cross-coupling reactions of 1-aryl-2-trimethylsilylethynes with aryl iodides, bromides, and chlorides as coupling partners, to furnish unsymmetrically disubstituted ethynes in moderate to excellent yields. Various aryl iodides were subjected to reaction under the optimized conditions with 5 mol % of Pd(PPh3)(2) and 50 mol % of CuCl. The steric properties of the aryl iodide proved more influential to the outcome of the cross-coupling reaction than electronic factors. In addition, we succeeded in synthesizing unsymmetrical diarylethynes using two different aryl iodides in one-pot. Furthermore, under the same reaction conditions with 10 mol % of PdCl2, 40 mol % of P(4-FC6H4)(3), and 50 mol % of CuCl as catalyst, we succeeded in synthesizing unsymmetrical diarylethynes from various aryl bromides. Finally, we explored reactions with aryl chlorides and duly discovered that unsymmetrical diarylethynes were obtainable in moderate to good yields when 10 mol % of Pd(OAc)(2), 10 mol % of (-)-DIOP, and 10 mol % of CuCl were used. These reactions proceed through a direct activation of a carbon silicon bond in alkynylsilanes by CuCl to generate the corresponding alkynylcopper species via transmetalation from silicon to copper. Mechanistic investigations on the reaction of alkynylsilanes with aryl bromides confirmed that the trimethylsilyl bromide generated in situ retarded both transmetalation steps between CuCl and alkynylsilane, and between palladium(II) species formed by oxidative addition and alkynylcopper species. (C) 2012 Elsevier Ltd. All rights reserved.

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  • Iron-Catalyzed Oxidation of Tertiary Amines: Synthesis of beta-1,3-Dicarbonyl Aldehydes by Three-Component C-C Couplings Reviewed

    Weiping Liu, Jinhua Liu, Daisuke Ogawa, Yasushi Nishihara, Xingwei Guo, Zhiping Li

    ORGANIC LETTERS   13 ( 23 )   6272 - 6275   2011.12

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    beta-1,3-Dicarbonyl aldehydes were synthesized by iron-catalyzed oxidative reactions between 1,3-dicarbonyl compounds and two molecules of tertiary amines in the presence of tert-butyl hydroperoxide (TBHP). alpha,beta-Unsaturated aldehydes generated by tertiary amine oxidation In situ act as key intermediates under mild reaction conditions.

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  • Copper-catalyzed Sila-Sonogashira-Hagihara Cross-coupling Reactions of Alkynylsilanes with Aryl Iodides under Palladium-free Conditions

    Yasushi Nishihara, Shintaro Noyori, Takeru Okamoto, Masato Suetsugu, Masayuki Iwasaki

    CHEMISTRY LETTERS   40 ( 9 )   972 - 974   2011.9

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    An efficient and inexpensive catalytic system using a readily available CuCl/PPh3 combination for the catalytic cross-coupling reactions of alkynylsilanes with a variety of aryl iodides affords unsymmetrical diarylethynes in good to excellent yields.

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  • Rh-Catalyzed Carbonylation of Arylzinc Compounds Yielding Symmetrical Diaryl Ketones by the Assistance of Oxidizing Agents

    Kana Kobayashi, Yugo Nishimura, Fuxing Gao, Kazuma Gotoh, Yasushi Nishihara, Kentaro Takagi

    JOURNAL OF ORGANIC CHEMISTRY   76 ( 6 )   1949 - 1952   2011.3

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    Carbonylative homocoupling of arylzinc compounds 1 using 1 atm of CO and 1,2-dibromoethane as an oxidant was achieved in the presence of Rh-dppf catalyst, affording symmetrical diaryl ketones in good yields. Under similar conditions, Pd or Ni catalysts induced oxidative homo coupling of 1 to yield biaryls instead. The beneficial catalysis by Rh in the carbonylation was presumed to stem from the facility by which the migration of the aryl ligand to CO at the Rh3+ intermediate occurred.

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  • Improvement in sulfur desorption of NOX storage and reduction catalysts using a Ba-Ti composite oxide

    Toshiyuki Tanaka, Ichirou Tajima, Yuichi Kato, Yasushi Nishihara, Hirofumi Shinjoh

    APPLIED CATALYSIS B-ENVIRONMENTAL   102 ( 3-4 )   620 - 626   2011.2

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    A Ba-Ti composite oxide was formed on a NOx storage and reduction catalyst via impregnation of a Ba-Ti precursor solution composed of H2O2 added to a complex prepared using the citric acid method. The structure of the Ba-Ti composite in solution was analyzed by chemical composition analysis and FT-Raman and UV-vis spectroscopy. MM2 calculations were performed to propose its chemical structure. Both Ba and Ti together were found to form a composite molecule in the solution. Furthermore, TEM-EDX and XRD analyses of the Ba-Ti composite oxide on the catalyst prepared by impregnation with the Ba-Ti composite aqueous solution revealed that Ba and Ti in the catalyst were highly dispersed at the nm scale. The formation of the Ba-Ti composite oxide on the NSR catalyst enhanced sulfur desorption efficiency and led to high-performance NOX conversion as a NOX storage and reduction activity catalyst after desulfation treatment. It was assumed that the existence of nano-scaled Ba compounds combined with Ti was efficient for the inhibition of the sintering of barium sulfate and its facile decomposition. It was found that dispersion of Ba compounds for NOX storage materials using a Ba-Ti complex solution is an efficient way to improve the durability of NSR catalysts. (C) 2011 Elsevier B.V. All rights reserved.

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  • Highly Regio- and Stereoselective Synthesis of Multialkylated Olefins through Carbozirconation of Alkynylboronates and Sequential Negishi and Suzuki-Miyaura Coupling Reactions

    Yasushi Nishihara, Yoshiaki Okada, Jiao Jiao, Masato Suetsugu, Ming-Tzu Lan, Megumi Kinoshita, Masayuki Iwasaki, Kentaro Takagi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   50 ( 37 )   8660 - 8664   2011

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  • Negishi Alkyl-Aryl Cross-Coupling Catalyzed by Rh: Efficiency of Novel Tripodal 3-Diphenylphosphino-2-(diphenylphosphino)methyl-2-methylpropyl Acetate Ligand

    Syogo Ejiri, Shunsuke Odo, Hideki Takahashi, Yugo Nishimura, Kazuma Gotoh, Yasushi Nishihara, Kentaro Takagi

    ORGANIC LETTERS   12 ( 8 )   1692 - 1695   2010.4

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    3-Diphenylphosphino-2-(diphenylphoshino)methyl-2-methylpropyl acetate acted as an efficient ligand for a Rh catalyst, achieving cross-coupling between arylzinc compounds bearing electron-withdrawing groups and alkyl electrophiles. The beneficial effect of the tripodal ligand and such aryl nucleophiles was discussed with regard to the specificity of the Rh catalysis.

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  • Enantioseparation of Doubly Functionalized Polar Norbornenes by HPLC and Their Ruthenium-Catalyzed Ring-Opening Metathesis Polymerization

    Yasushi Nishihara, Yukiko Doi, Seisuke Izawa, Horng-Yi Li, Yoshiaki Inoue, Masaaki Kojima, Jwu-Ting Chen, Kentaro Takagi

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   48 ( 2 )   485 - 491   2010.1

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    DOI: 10.1002/pola.23781

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  • Palladium- and base-free synthesis of conjugated ynones by cross-coupling reactions of alkynylboronates with acid chlorides mediated by CuCl

    Yasushi Nishihara, Daisuke Saito, Eiji Inoue, Yoshiaki Okada, Mikihiro Miyazaki, Yoshiaki Inoue, Kentaro Takagi

    TETRAHEDRON LETTERS   51 ( 2 )   306 - 308   2010.1

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    Alkynylboronates can be employed as a practical and versatile precursor for a variety of pi-conjugated organic compounds. In the presence of Cu(I) salt, cross-coupling reactions of acid chlorides with alkynylboronates giving rise to the corresponding conjugated ynones takes place readily in aprotic polar solvents such as DMI under neutral conditions. (C) 2009 Elsevier Ltd. All rights reserved.

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  • Development of New Methodology for Bond Activation by Transition Metal Complexes and Their Application toward Functional Molecule Synthesis

    Yasushi Nishihara

    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN   67 ( 9 )   889 - 897   2009.9

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    In this review, the results of studies on new methodology for bond activation by using transition metal complexes are described, in order to realize the expeditious and selective synthesis of organic compounds. Carbon-carbon bond formation reactions, accompanying with cleavage of unactivated bonds such as carbon-carbon, carbon-boron, and carbon-silicon bonds, are reported. This review involves, for examples, the new synthetic methodology to introduce both cyano and ester groups (cyanoesterification) via the C-C bond activation, regio- and stereoselective synthesis multi-substituted olefins mediated a zirconocene complex via the C-B bond activation, and cross-coupling reaction of alkynylsilanes activated by a copper salt via the C-Si bond cleavage. Each reaction can be applicable to synthesis of functional molecules such as opto-electronic materials, an anti-cancer agent, and liquid crystalline compounds.

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  • Palladium/copper-catalyzed sila-Sonogashira reactions of aryl iodides with alkynylsilanes via a direct C-Si bond activation

    Yasushi Nishihara, Eiji Inoue, Daisuke Ogawa, Yoshiaki Okada, Shintaro Noyori, Kentaro Takagi

    TETRAHEDRON LETTERS   50 ( 32 )   4643 - 4646   2009.8

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    The palladium-catalyzed cross-coupling reactions of aryl iodides with alkynylsilanes in the presence of a substoichiometric amount (50 mol %) of copper(I) chloride as an activator in DMF under strictly non-basic reaction conditions afford the corresponding unsymmetrical diarylethynes in moderate to excellent yields. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on the aromatic ring are compatible. (C) 2009 Elsevier Ltd. All rights reserved.

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  • Regio- and Stereoselective Synthesis of Multisubstituted Vinylsilanes via Zirconacycles

    Yasushi Nishihara, Daisuke Saito, Kenki Tanemura, Shintaro Noyori, Kentaro Takagi

    ORGANIC LETTERS   11 ( 16 )   3546 - 3549   2009.8

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    A series of novel multisubstituted vinylsilanes are prepared regio- and stereoselectively by carbozirconation of various alkynylsilanes through zirconacycles such as zirconacyclopropenes and zirconacyclopentenes and the subsequent transformation of the formed alkenylzirconocene complexes.

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  • Comparative reactivity of triorganosilanes, HSi(OEt)(3) and HSiEt3, with IrCl(CO)(PPh3)(2). Formation of IrCl(H)(2)(CO)(PPh3)(2) or Ir(H)(2)(SiEt3)(CO)(PPh3)(2) depending on the substituents at Si

    Yasushi Nishihara, Miwa Takemura, Kohtaro Osakada

    INORGANICA CHIMICA ACTA   362 ( 8 )   2951 - 2956   2009.6

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    Reaction of HSi(OEt)(3) with IrCl(CO)(PPh3)(2) (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)(3)}(CO)(PPh3)(2) (1), which is observed by the H-1 and P-31{H-1} NMR spectra of the reaction mixture. The same reaction, but in 20:1 molar ratio at 50 degrees C for 24 h produces IrCl(H)(2)(CO)(PPh3)(2) (2) rather than the expected product Ir(H)(2){Si(OEt)(3)}(CO)(PPh3)(2) (3) that was previously reported to be formed by this reaction. Accompanying formation of Si(OEt)(4), (EtO)(3)SiOSi(OEt)(3), and (EtO)(2)HSiOSi(OEt)(3) is observed. On the other hand, trialkylhydrosilane HSiEt3 reacts with IrCl(CO)(PPh3)(2) (10:1 molar ratio) at 80 degrees C for 84 h to give Ir(H)(2)(SiEt3)(CO)(PPh3)(2) (4) in a high yield, accompanying with a release of ClSiEt3. (C) 2009 Elsevier B.V. All rights reserved.

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  • Rh-Catalyzed Negishi Alkyl-Aryl Cross-Coupling Leading to alpha- or beta-Phosphoryl-Substituted Alkylarenes

    Hideki Takahashi, Shinya Inagaki, Naoko Yoshii, Fuxing Gao, Yasushi Nishihara, Kentaro Takagi

    JOURNAL OF ORGANIC CHEMISTRY   74 ( 7 )   2794 - 2797   2009.4

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    The catalytic cross-coupling between ArZnX and ICH(2)(CH(2))(n)P(O)(OEt)(2) (n = 0-3) has been investigated to determine the utility of the Rh catalyst during the alkyl-aryl cross-coupling and to develop a new synthetic method for phosphoryl-substituted alkylarenes. Rh-dppf exhibits an excellent catalytic activity for the reaction with the alkylphosphonate of n = 1, whereas for the reaction with those of n = 2 or 3, P-hydride elimination mainly takes place. As for the reaction with an alkylphosphonate of n = 0, a polarity inversion of the coupling components is necessary in order to provide the coupling products; the phosphoryl analogue of the Reformatsky reagent and ArI give the cross-coupling products in good yields through the catalysis by Rh-dppf.

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  • Photocatalytic Activities of Graphitic Carbon Nitride Powder for Water Reduction and Oxidation under Visible Light

    Kazuhiko Maeda, Xinchen Wang, Yasushi Nishihara, Daling Lu, Markus Antonietti, Kazunari Domen

    JOURNAL OF PHYSICAL CHEMISTRY C   113 ( 12 )   4940 - 4947   2009.3

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    Graphitic carbon nitride (g-C(3)N(4)) with a band gap of 2.7 eV is studied as a nonmetallic photocatalyst for H(2) or O(2) evolution from water under ultraviolet (UV) and visible light. The g-C(3)N(4) catalyst exhibits activities for water reduction into H(2) or water oxidation into O(2) in the presence of a proper sacrificial electron donor or acceptor, respectively, even without the need for precious metal cocatalysts. When bis(1,5-cyclooctadiene)platinum complex [Pt(cod)(2)] (a nonionic complex) is used as a precursor of Pt cocatalyst instead of H(2)PtCl(6) (an ionic complex), enhanced H(2)) evolution activity is acquired. This difference in activity is primarily due to the better dispersion of Pt nanoparticles on g-C(3)N(4), which is considered to originate from the better access of Pt(cod)(2) to the g-C(3)N(4) surface, as compared to that of H(2)PtCl(6) in the preparation process. Unmodified g-C(3)N(4) produces O(2) from an aqueous silver nitrate solution upon UV irradiation (lambda &gt; 300 nm), although N(2), release due to self-decomposition of g-C(3)N(4) by photogenerated holes takes place. Modification of g-C(3)N(4) with RuO(2), improves not only O(2) evolution activity but also stability against the self-decomposition, resulting in stable visible-light-driven O(2) evolution (lambda &gt; 420 nm).

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  • Synthesis and Ion Conductive Characteristics of Inorganic-Organic Hybrid Polymers Bearing a Tetraarylpentaborate Unit

    Yasushi Nishihara, Mikihiro Miyazaki, Yasumasa Tomita, Yuuki Kadono, Kentaro Takagi

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   46 ( 23 )   7913 - 7918   2008.12

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    DOI: 10.1002/pola.23070

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  • Sila-Sonogashira Cross-Coupling Reactions of Activated Aryl Chlorides with Alkynylsilanes

    Yasushi Nishihara, Eiji Inoue, Yoshiaki Okada, Kentaro Takagi

    SYNLETT   ( 19 )   3041 - 3045   2008.12

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    The palladium/copper-cocatalyzed sila-Sonogashira cross-coupling reactions of activated aryl chlorides with alkynylsilanes under strictly nonbasic conditions yield the unsymmetrical diarylethynes in moderate to good yields.

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  • Synthesis, characterization, and thermal properties of ring-opening metathesis polynorbornenes and their hydrogenated derivatives bearing various ester and cyano groups

    Yasushi Nishihara, Seisuke Izawa, Yoshiaki Inoue, Yuushou Nakayama, Takeshi Shiono, Kentaro Takagi

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   46 ( 10 )   3314 - 3325   2008.5

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    Doubly functionalized polar norbornenes 3a-3g substituted by both a variety of ester and cyano groups were polymerized by ring-opening metathesis polymerization (ROMP) with a Ru carbene complex 2 bearing 3-bromopyridine as a ligand (third generation Grubbs' catalyst) in a living manner. The successive hydrogenation of the main-chain double bond in the synthesized living ROMP polymers 4a-4g with a hydridoruthenium complex was exploited. The comparison of thermal properties of a series of ring-opening metathesis polymers 4a-4g with those of their hydrogenated derivatives 5a-5g revealed the decrease of glass transition temperatures (T-g) but little change of the 5% decomposition temperature (T-d(5)). In all cases examined in this study, a decrease of T-g by hydrogenation was around 20-40 degrees C, regardless of the ester substitutents. In the presence of the additional PCy3, triethylamine, and methanol after complete consumption of monomer 3a under the living ROMP condition, the tandem ROMP-hydrogenation of the resulting polymer 4a generated in situ was attained under a H-2 (9.8 MPa) atmosphere at 80 degrees C to afford the hydrogenated polymer 5a, retaining the narrow polydispersity of 1.03. (C) 2008 Wiley Periodicals, Inc.

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  • Pd-P(t-BU)(3)-catalyzed consecutive cross-coupling of p-phenylenedizinc compound with two different electrophiles leading to unsymmetrically 1,4-disubstituted benzenes

    Takahiro Kawamoto, Shogo Ejiri, Kana Kobayashi, Shunsuke Odo, Yasushi Nishihara, Kentaro Takagi

    JOURNAL OF ORGANIC CHEMISTRY   73 ( 4 )   1601 - 1604   2008.2

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    Pd-P(t-BU)(3) was found to be a chemoselective catalyst for the reaction of p-phenylenedizinc compound with equimolar amounts of carbon electrophiles to afford the single cross-coupling products in good yields, effectively suppressing the formation of double cross-coupling products. The subsequent additions of other electrophiles to the resulting solutions caused the second cross-coupling of the incipient products to take place, achieving a novel and efficient one-pot synthesis of unsymmetrically 1,4-disubstituted benzenes. The origin of the observed high chemoselectivity was speculated.

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  • Zirconocene-mediated highly regio- and stereoselective synthesis of multisubstituted olefins starting from 1-alkynylboronates Reviewed

    Yasushi Nishihara, Mitsuru Miyasaka, Masanori Okamoto, Hideki Takahashi, Eiji Inoue, Kenki Tanemura, Kentaro Takagi

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   129 ( 42 )   12634 - +   2007.10

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    Multisubstituted olefins are efficiently prepared by the zirconocene-mediated regio- and stereoselective coupling between 1alkynylboronates and ethylene, followed by sequential transformation in moderate to high yields. The proper combination of substrates and reaction conditions is important for high yields. The synthesis of various tetra substituted alkenes in a regio- and stereocontrolled manner is described. This methodology has been applied to the synthesis of (Z )-tamoxifen in a concise, regio and stereoselective manner. This multicomponent coupling strategy involves the characteristics of 1-alkynylboronates toward high selectivities followed by palladium(O)-mediated cross-coupling with aryl halides.

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  • Preparation, structures, and thermal reactivity of alkoxycarbonyl(cyano)palladium(II) complexes trans-Pd(COOR)(CN)(PPh3)(2) (R = Me, Et, Pr-n, Pr-i, Bu-n, Bu-t, and Bn) as intermediates of the palladium-catalyzed cyanoesterification of norbornene derivatives

    Yasushi Nishihara, Mitsuru Miyasaka, Yoshiaki Inoue, Tomoka Yamaguchi, Masaaki Kojima, Kentaro Takagi

    ORGANOMETALLICS   26 ( 16 )   4054 - 4060   2007.7

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    Alkoxycarbonyl(cyano)palladium(II) complexes trans-Pd(COOR)(CN)(PPh3)(2) (1, R = Me; 2, R = Et; 3, R = Pr-n; 4, R = Pr-i; 5, R = Bu-n; 6, R = Bu-t; 7, R = Bn) are prepared via oxidative addition of the corresponding cyanoformates to Pd(PPh3)(4) in toluene at room temperature or 50 degrees C and characterized by means of NMR (H-1, C-13{H-1}, and P-31{H-1}) and IR spectroscopy as well as elemental analyses. X-ray crystallography of 3, 4, and 6 showed a square-planar coordination around the Pd center that is bonded to alkoxycarbonyl and cyano ligands in the trans configuration. The Pd-CN and Pd-COOR bonds in 1, 3, 4, and 6 are similar to those of the cyanopalladium(II) and alkoxycarbonylpalladium(II) complexes reported to date. On reaction of Pd(PPh3)(4) with phenyl cyanoformate a thermally induced ligand exchange takes place to afford the dicyanopalladium(II) complex, trans-Pd(CN)(2)(PPh3)(2) (8). Complex 2 is able to catalyze the reaction of norbornadiene with ethyl cyanoformate to produce (2R*,3S*)-ethyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (13) and is recovered after the reaction. This observation supports the identification of alkoxycarbonyl(cyano)palladium(II) complexes as intermediates in the catalytic cycle of cyanoesterification of norbornene derivatives.

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  • 1,1,3,3-Tetrakis(alkylthio)-1,3-dilithio-2-silapropanes: useful reagents for the synthesis of polysilacycloalkanes via dianionic ring formation

    Masaki Shimizu, Masayuki Iwakubo, Yasushi Nishihara, Katsunari Oda, Tamejiro Hiyama

    ARKIVOC   29 - 48   2007

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    Treatment of 1,1,3,3-tetrakis(alkylthio)-2-silapropanes with t-BuLi in THF at -40 degrees C generated 1,1,3,3-tetrakis(alkylthio)-1,3-dilithio-2-silapropanes which reacted with various bifunctional chlorosilanes to give the corresponding 4- to 7-membered polysilacycloalkanes in moderate to good yields. Furthermore, double alkylation of the dilithiated silanes with bis(halomethyl)diorganosilanes or dihaloalkanes was found to proceed smoothly giving rise to 1,4-disilacyclohexanes or silacycloalkanes in good yields, respectively, in THF and an aprotic polar co-solvent such as hexamethylphosphoric triamide (HMPA) or 1,1,3,3-tetramethylurea (TMU). The sulfenyl groups in the cyclized products were smoothly removed by radical reduction with tributyltin hydride.

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  • Living ring-opening metathesis polymerization of Exo-norbornenes bearing both cyano and ester functionalities by a well-defined ruthenium catalyst

    Yasushi Nishihara, Yoshiaki Inoue, Akira T. Saito, Yuushou Nakayama, Takeshi Shiono, Kentaro Takagi

    POLYMER JOURNAL   39 ( 4 )   318 - 329   2007

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    Exo-ethyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (A) and exo-(n)butyl 3-cyanobicyclo[2.2.1]-hept-5-ene-2-carboxylate (B) bearing both cyano and ester groups were subjected to homopolymerization by ring-opening metathesis polymerization with a well-defined Ru catalyst, (H(2)IMes)(3-bromopyridine)(2)Cl2Ru=CHPh (3) (H(2)IMes = N,N'-bis(mesityl)-4,5-dihydroimidazol-2-ylidine) at low temperature. The characterization of the synthesized homopolymers by GPC analyses showed a value of a number-average molecular weight (Mn) as high as 296,000 and a narrow polydispersity index (&lt; 1.06). The results imply that the initiator 3 had a compatibility of the polar functional groups and promoted fairly well-defined living polymerization. The glass transition temperatures of the homopolymers obtained from monomer A were significantly higher than those observed for polymers from monomer B obtained under the same reaction conditions. The rates of homopolymerizations of monomer A, B, and the parent norbornene (C) were determined by the monitoring the consumption of the monomers by the H-1 NMR spectra. It was revealed that the polymerization rate for the homopolymerization of monomer A was almost same as that of monomer B, but much slower than that of C. On the basis of the successful homopolymerization, the synthesis of block and random copolymers derived from monomers A, B, and C via living polymerization using catalyst 3 was also accomplished.

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  • Cyanoesterification of norbornenes catalyzed by palladium: facile synthetic methodology to introduce cyano and ester functionalities via direct carbon-carbon bond cleavage of cyanoformates

    Yasushi Nishihara, Yoshiaki Inoue, Seisuke Izawa, Mitsuru Miyasaka, Kenki Tanemura, Kiyohiko Nakajima, Kentaro Takagi

    TETRAHEDRON   62 ( 42 )   9872 - 9882   2006.10

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    Addition of cyanoformates (NC-COOR) to norbornene at 110 degrees C in the presence of Pd(PPh(3))(4) (10 mol %) as a catalyst affords with high selectivity the corresponding doubly functionalized polar norbornane derivatives bearing both cyano and ester groups. By using benzonorbornadiene and norbornadienes as the substrates, the reaction can be extended to synthesis of various functionalized norbornene derivatives in moderate to excellent yields. In most cases alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, and benzyl in the ester functionalities are applicable to the reactions. Oxidative addition of cyanoformates to Pd(0), insertion of norbornenes, and reductive elimination of the corresponding adducts constitute the proposed catalysis pathway. (c) 2006 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.tet.2006.08.025

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  • Comparative reactivity of exo- and endo-isomers in the Ru-initiated ring-opening metathesis polymerization of doubly functionalized norbornenes with both cyano and ester groups

    Yasushi Nishihara, Yoshiaki Inoue, Yuushou Nakayama, Takeshi Shiono, Kentaro Takagi

    MACROMOLECULES   39 ( 22 )   7458 - 7460   2006.10

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    DOI: 10.1021/ma061781c

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  • Novel Rh catalysis in cross-coupling between alkyl halides and arylzinc compounds possessing ortho-COX (X = OR, NMe2, or Ph) groups

    Hideki Takahashi, Shinya Inagaki, Yasushi Nishihara, Takanori Shibata, Kentaro Takagi

    ORGANIC LETTERS   8 ( 14 )   3037 - 3040   2006.7

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    Rh-dppf was found to be an efficient catalyst for the cross-coupling between primary alkyl halides bearing beta-hydrogens and arylzinc compounds possessing carbonyl groups such as ester, amide, or ketone at the ortho position. Various functional groups such as ester, nitrile, or acyloxylate moieties on the halides were tolerated under the catalysis conditions. Arylzinc compounds free of ortho-carbonyl groups reacted well with ethyl 3-iodopropanoate, suggesting that the essential intramolecular interaction between carbonyl groups and Rh promotes the reductive elimination.

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  • Synthesis of functionalized benzylsilanes from arylzinc compounds and (iodomethyl)trimethylsilane by means of a novel Rh catalysis

    H Takahashi, KM Hossain, Y Nishihara, T Shibata, K Takagi

    JOURNAL OF ORGANIC CHEMISTRY   71 ( 2 )   671 - 675   2006.1

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    The catalytic activity of a Rh complex in cross-coupling between ArZnI and TMSCH2I was examined in which the Rh complex, generated in situ from [RhCl(1,5-cyclooctadiene)](2) and 1,1'-bis(diphenylphosphino)ferrocene, exhibited excellent catalytic activity for the production of various functionalized benzylsilanes in good yields. From P-31 NMR studies of various solutions containing several of the reaction components, confirmation of the rapid and quantitative transfer of aryl groups from ArZnI to the Rh complex to form arylrhodium species was ascertained. A catalytic cycle, commencing with the transmetalation, was thus proposed for the reaction.

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  • Synthesis of symmetrical 1,3-butadiynes by homocoupling reactions of alkynylboronates mediated by a copper salt

    Y Nishihara, M Okamoto, Y Inoue, M Miyazaki, M Miyasaka, K Takagi

    TETRAHEDRON LETTERS   46 ( 50 )   8661 - 8664   2005.12

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    Alkynylboronates are employed as a practical and versatile precursor for a variety of it-conjugated organic compounds. In the presence of a Cu(I) or Cu(II) salt, transformation of alkynylboronates into the corresponding 1,3-diynes upon exposure to air takes place readily in aprotic polar solvents such as DMI. (c) 2005 Elsevier Ltd. All rights reserved.

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  • Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes

    M Itazaki, Y Nishihara, H Takimoto, C Yoda, K Osakada

    JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL   241 ( 1-2 )   65 - 71   2005.11

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    2-Phenyl-1-methylenecyclopropane is isometized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh3)(3) and RhH(PPh3)(4). The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh3)(3). RhH(CO)(PPh3)(3) promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[eta(3)-anti-CH2C{C(=CH2)Ph}CHCH3](PPh3)(2) (2) at 50 degrees C and Rh{kappa(1),eta(2)-CH2CH(Ph)C(=CH2)CH=CH2}(CO)(PPh3)(2) (3) at -35 degrees C. X-ray crystallography of 2 shows the pi-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed. (c) 2005 Elsevier B.V All rights reserved.

    DOI: 10.1016/j.molcata.2005.06.045

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  • Preparation of Pd(PPh2H)(2)(PPh3)(2) and its role as a precursor of a dinuclear complex with bridging phosphide ligands

    M Itazaki, Y Nishihara, K Osakada

    TRANSITION METAL CHEMISTRY   30 ( 7 )   828 - 830   2005.10

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    Reaction of PPh2H with Pd(PPh3)(4) in a 4:1 molar ratio produced the Pd complex with two diphenylphosphine ligands, Pd(PPh2H)(2)(PPh3)(2) (1). Complex (1) was characterized by n.m.r. (H-1 and P-31{H-1}) spectra as well as by elemental analysis. Reaction of (1) with RhCl(PPh3)(3) yielded a Pd-Rh heterobimetallic complex with bridging phosphide ligands, formulated as [(Ph3P)(2)Pd(mu-PPh2)(2)Rh(PPh3)(2)]Cl (2).

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  • Hexanuclear Pt complexes composed of two cyclic triplatinum units connected with 1,4-diphenylene and 1,1 '-ferrocenylene spacer

    M Itazaki, O Kitami, M Tanabe, Y Nishihara, K Osakada

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   690 ( 17 )   3957 - 3962   2005.9

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    1,4-Bis(dimethylsilyl) benzene reacted with [Pt3H(PEt3)(3)(mu-PPh2)(3)] at room temperature to yield trinuclear Pt complex [Pt-3(SiMe2C6H4SiMe2H)(PEt3)(2) (mu-PPh2)(3)] (1a). Heating a solution containing an equimolar mixture of [Pt3H(PEt3)(3)mu PPh2)(3)] and 1a at 60 degrees C produced a hexanuclear Pt complex [(PEt3)(2)( mu-PPh2)(3)Pt-3(SiMe2C6H4SiMe2)Pt-3(PEt3)(2)(mu-PPh2)(3)] (2a). Complex 1a was characterized by X-ray crystallography and NMR spectroscopy, while the structure of 2a was determined by X-ray crystallography of single crystals containing 2a and [Pt3H2(PEt3)(2)(mu-PPh2)(4)] in 1:1 ratio. [Pt-3(SiMe(2)fcSiMe(2)H)(PEt3)(2)( mu-PPh2)(3)] (fc = Fe(eta(5)-C5H4)(2)) (1b) and [(PEt3)(2) (mu-PPh2)(3)Pt-3(SiMe(2)fcSiMe(2))Pt-3(PEt3)(2)(mu-PPh2)(3)] (2b) were obtained similarly from the reactions of 1,1 '-bis(dimethyisilyl)ferrocene with [Pt3H(PEt3)(3)(mu-PPh2)(3)] and characterized by NMR spectroscopy and elemental analyses. (c) 2005 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.jorganchem.2005.05.030

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  • Room-temperature palladium-catalyzed and copper(I)-mediated coupling reactions of acid chlorides with boronic acids under neutral conditions

    Y Nishihara, Y Inoue, M Fujisawa, K Takagi

    SYNLETT   ( 15 )   2309 - 2312   2005.9

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    The palladium-catalyzed cross-coupling reactions of acid chlorides with arylboronic acids in the presence of copper(l) thiophene-2-carboxylate (CuTC) as an activator under strictly nonbasic and mild reaction conditions afford the unsymmetrical ketones in moderate to excellent yields. A wide range of substrates bearing an electron-donating or an electron-withdrawing substituent on the aromatic ring is compatible.

    DOI: 10.1055/s-2005-872661

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  • Arylplatinum complexes with arylboronate ligands. Their preparation, structure, and relevance to transmetalation

    Pantcheva, I, Y Nishihara, K Osakada

    ORGANOMETALLICS   24 ( 16 )   3815 - 3817   2005.8

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    The reactions of arylboronic acids with transPtPh(I)(PMe2Ph)(2) afford new arylboronato platinum complexes, trans-PtPh(OB(OH)Ar)(PMe2Ph)(2), and diarylplatinum complexes, trans-PtPh(Ar)(PMe2Ph)(2).

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  • Selective C-C bond activation of 2-aryl-1-methylenecyclopropanes promoted by Ir(I) and Rh(I) hydrido complexes. Mechanism of ring-opening isomerization of the strained molecules

    Y Nishihara, C Yoda, M Itazaki, K Osakada

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   78 ( 8 )   1469 - 1480   2005.8

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    [IrH(CO)(PPh3)(3)] promotes ring opening of 2-phenyl-l-methylenecyclopropane at room temperature to produce the Ir complex with a chelating 2-phenyl-3-butenyl ligand, [Ir{eta(2)-CH2CH(Ph)CH=CH2-kappa C-1}(CO)(PPh3)(2)] (1). The reaction of excess 2-phenyl-l-methylenecyclopropane with [IrH(CO)(PPh3)(3)] at 50 degrees C yields [Ir{eta(2)-(o-C6H4)CH(Me)CH= CH2-kappa C-1)(CO)(PPh3)(2)] (2), accompanied by the formation of 1-phenyl-1,3-butadiene and 2-phenyl-1.3-butadiene. 2,2-Diphenyl-l-methylenecyclopropane reacts with [IrH(CO)(PPh3)(2)] to afford [Ir{eta(2)-CH2-CPh2CH=CH2-kappa C-1}(CO)-(PPh3)(2)] (3) at 50 degrees C and [Ir{eta(2)-(o-C6H4)CMe(Ph)CH=CH2-kappa C-1)(CO)(PPh3)(2)] (4) at 100 degrees C. Heating a solution of 3 at 100 degrees C also forms 4 quantitatively. X-ray crystallography of 3 reveals a penta-coordinated structure around the Ir center bonded to a chelating 2,2-diphenyl-3-butenyl ligand. The reactions of 2,2-diphenyl-l-methylenecyclopropane and of 2,2-di(4-fluorophenyt)-1-methylenecyclopropane with [RhH(CO)(PPh3)(3)] at room temperature yield [Rh{eta(2)- CH2CAr2CH=CH2-kappa C-1}(CO)(PPh3)(2)] (5a: Ar = Ph, 5b: Ar = C6H4-F-4). The reactions at 50 degrees C cause ring opening of the substrate and orthometalation of the phenyl group to afford [Rh{eta(2)-(o-C6H4)CMe(Ph)CH=CH2-kappa C-1}-(CO)(PPh3)(2)](6a) and [Rh{eta(2)-(o-C6H3-F-4)CMe(C6H4-F-4)CH=CH2-kappa C-1}(CO)(PPh3)(2)](6b), respectively. Formation of 1,1-diaryl-1,3-butadiene is observed during the reaction. Heating a solution of 5a at 50 degrees C produces 1,1-diphenyl-1,3-butadiene and an allylrhodium complex, 8, rather than 6a, although the reaction of excess 2,2-diphenyt-1-methylenecyclopropane with 5a at 50 degrees C affords 6a in 60 %. The mechanisms of the above reactions are discussed based on the products and reaction rates. Coordination of P(OMe)(3) to the Rh center of 5a causes insertion of the CO ligand into the Rh-C bond to afford [Rh{eta(2)-CO-CH2CPh2CH=CH2-kappa C-1}(P(OMe)(3))(3)] (7).

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  • Dinuclear Pt(II) and Pd(I) complexes with bridging PPh2 ligands from the reaction of PPh2H with zero-valent complexes of these metals

    M Tanabe, M Itazaki, O Kitami, Y Nishihara, K Osakada

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   78 ( 7 )   1288 - 1290   2005.7

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    Reactions of PPh2H with [M(PCy3)(2)] (M = Pt, Pd) produce the dinuclear complexes with bridging PPh2 ligands of these metals, [{Pt(H)(PCy3)}(2)(mu-PPh2)(2)] and [{Pd-(PCy3)}(2)(mu-PPh2)(2)], respectively.

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  • Palladium-catalyzed cyanoesterification of norbornenes with cyanoformates via the NC-Pd-COOR (R = Me and Et) intermediate

    Y Nishihara, Y Inoue, M Itazaki, K Takagi

    ORGANIC LETTERS   7 ( 13 )   2639 - 2641   2005.6

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    Palladium-catalyzed cyanoesterification of norbornenes proceeds stereoselectively via NC-Pd-COOR (R = Me and Et) complexes as intermediates.

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  • Diarylpalladium complexes with a cis structure. Formation via transmetalation of arylboronic acids with an aryliodopalladium complex and intramolecular coupling of the aryl ligands, affording unsymmetrical biaryls

    K Osakada, H Onodera, Y Nishihara

    ORGANOMETALLICS   24 ( 2 )   190 - 192   2005.1

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    (2,4,6-Trifluorophenyl)- and (2,6-difluorophenyl)boronic acids react with PdI(C6H4O4-Me)(tmen) (tmen = N,N,N',N'-tetramethylethylenediamine) in the presence of Ag2O to produce cis-diarylpalladium complexes with a tmen ligand via intermolecular transfer of the fluorophenyl group from B to Pd. The isolated complexes undergo coupling of the two aryl ligands upon heating the solution to 45-60 degreesC to afford unsymmetrical biaryls.

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  • C-C and C-H bond activation of dialkylmethylenecyclopropane promoted by rhodium and iridium complexes. Preparation and structures of M(eta(1):eta(2)-CH2CR2CH=CH2)(CO)(PPh3)(2) and trans-M(CH=CHCMeR2)(CO)(PPh3)(2) (M = Rh, Ir, R = CH2CH2Ph)

    M Itazaki, C Yoda, Y Nishihara, K Osakada

    ORGANOMETALLICS   23 ( 23 )   5402 - 5409   2004.11

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    2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh3)(3) at room temperature and with IrH(CO)(PPh3)(3) at 70 degreesC to form the 3-butenyl complexes of these metals, M{eta(1):eta(2)-CH2C(CH2CH2Ph)(2)CH=CH2}(CO)(PPh3)(2) (1, M = Rh; 2, M = Ir). Heating 1 at 55 degreesC liberates 1,1-bis(2-phenylethyl)-1,3-butadiene, while the thermal reaction of 2 at 110 degreesC forms a mixture of 3-methyl-3-vinyl-1,5-diphenyl-1-pentene (48% NMR yield) and 3-methyl-3-vinyl-1,5-diphenylpentane (15% NMR yield). The reactions of excess amounts of 2,2-bis(2-phenylethyl)-1-methylenecyclopropane with RhH(CO)(PPh3)(3) at 55 degreesC and with IrH(CO)(PPh3)(3) at 115 degreesC afford the alkenyl complexes trans-Rh{(Z)-CH=CHC(CH2CH2Ph)(2)CH3}-(CO)(PPh3)(2) (3) and trans-Ir{(E)-CH=CHC(CH2CH2Ph)(2)CH3}(CO)(PPh3)(2) (4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HCequivalent toCC(CH2CH2Ph)(2)CH3 reacts with MH(CO)(PPh3)(3) (M = Rh, Ir) to afford the alkynyl complexes trans-M{Cequivalent toCC(CH2CH2Ph)(2)CH3}(CO)(PPh3)(2) (5, M = Rh; 6, M = Ir) via oxidative addition of the C(alkyne)-H bond to the metal center and subsequent elimination of H-2.

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  • Cationic Rh complexes with novel spiro tetraarylpentaborate anions prepared from arylboronic acids and aryloxorhodium complexes

    Y Nishihara, K Nara, Y Nishide, K Osakada

    DALTON TRANSACTIONS   ( 9 )   1366 - 1375   2004.5

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    Ar-B(OH)(2) (1a: Ar = C6H4OMe-4, 1b: Ar = C6H3Me2-2,6) react immediately with Rh(OC6H4Me-4)(PMe3)(3) (2) in 5 : 1 molar ratio at room temperature to generate [Rh(PMe3)(4)](+)[B5O6Ar4](-) (3a: Ar C6H4OMe-4, 3b: Ar = C6H3Me2- 2,6). p-Cresol (92%/Rh), anisole (80%/Rh) and H2O (364%/Rh) are formed from 1a and 2. The reaction of 1a with 2 for 24 h produces [Rh(PMe3)(4)](+)[B5O6(OH)(4)](-) (4) as a yellow solid. This is attributed to hydrolytic dearylation of once formed 3a because the direct reaction of 3a with excess H2O forms 4. An equimolar reaction of 2 with phenylboroxine (PhBO)(3) causes transfer of the 4-methylphenoxo ligand from rhodium to boron to produce [Rh(PMe3)(4)](+) [B3O3Ph3(OC6H4Me-4)](-) (5). Arylboronic acids 1a and 1b react with Rh(OC6H4Me-4)(PR3)(3) (6: R = Et, 8: R = Ph) and with Rh(OC6Me-4)(cod)(PR3) (11: R = Pr-i, 12: R = Ph) to form [Rh(PR3)(4)](+)[B5O6Ar4](-) (7a: R = Et, Ar = C6H4OMe-4, 7b: R = Et, Ar = C6H3Me2-2,6, 9a: R = Ph, Ar = C6H3Me2-2,6) and [Rh(cod)(PR3)(L)](+)[B5O6Ar4](-) (13b: R = Pr-i, L = acetone, Ar = C6H3Me2-2,6,14a: R = Ph L = PPh3, Ar = C6H4OMe-4, 14b: R = Ph, L = PPh3, Ar - C6H3Me2-2,6), respectively. Hydrolysis of 14a yields [Rh(cod)(PPh3)(2)](+)[B5O6(OH)(4)](-) (15) quantitatively.

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  • Stereodivergent syntheses of (Z)- and (E)-alkenylsilanes via hydrosilylation of terminal alkynes catalyzed by rhodium(I) iodide complexes and application to silicon-containing polymer syntheses

    A Mori, E Takahisa, Y Yamamura, T Kato, AP Mudalige, H Kajiro, K Hirabayashi, Y Nishihara, T Hiyama

    ORGANOMETALLICS   23 ( 8 )   1755 - 1765   2004.4

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    RhI(PPh3)(3) or [RhI(cod)](2) (cod = 1,5-cyclooctadiene) as a catalyst delivers both (Z)- and (E)-alkenylsilanes in the stereodivergent hydrosilylation of terminal alkynes with heteroatom-substituted organosilane reagents. Treatment of the rhodium catalyst and the silane reagent followed by addition of terminal alkyne at room temperature leads to (Z)-silanes, while addition of the silane and the alkyne to the rhodium catalyst in one portion and heating at 60 degreesC affords (E)-silanes highly selectively. The obtained (E)- and (Z)-alkenylsilanes bearing heteroatom substituents on the silicon atom are subjected to the palladium-catalyzed cross-coupling reaction with aryl halides to form a carbon-carbon bond with retention of stereochemistry. The stereodivergent hydrosilylations are applied to the polyaddition with bifunctional alkynes (1,3- and 1,4-diethynylbenzene) and silanes (1,3- or 1,4-bis(dimethyl-silyl)benzene), giving silicon-containing polymers, poly(aryleneethenylenesilylene)s, in highly stereocontrolled manners. A fluorine-containing silicon reagent bearing a 3,3,3-trifluoropropyl group is also subjected to the polymerization, in which [RhI(cod)12 is found to be an efficient catalyst. Measurement of UV-vis absorption/emission spectra and several. thermal analyses of the polymers are also conducted.

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  • Syntheses of dinuclear and trinuclear hydridoplatinum complexes with bridging phosphido Ligands [Pt2H2(mu-PR2)(2)(PEt3)(2)] (R = Bu-t, Ph) and [Pt3H2(mu-PPh2)(4)(PEt3)(2)]. Characterization of the triangular intermediate [Pt3H(mu-PPh2)(3)(PEt3)(3)] and its chemical properties

    M Itazaki, Y Nishihara, K Osakada

    ORGANOMETALLICS   23 ( 7 )   1610 - 1621   2004.3

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    The reaction of Ph2PH with Pt(PEt3)(3) in 2:1 molar ratio produces the linear triplatinum Complex [Pt3H2(mu-PPh2)(4)(PEt3)(2)] (1). X-ray crystallography of I shows the structure of the complex with two PEt3 ligands at anti positions, while it exists as a mixture of the isomers with PEt3 at anti and syn positions. Pt(PEt3)(3) reacts with equimolar Ph2PH to afford the dinuclear complex [Pt2H2(mu-PPh2)(2)(PEt3)(2)] (2) and the cyclic trinuclear complex [Pt3H(mu-PPh2)3(PEt3)31 (3) depending on the reaction conditions. A dinuclear platinum(II) complex with a structure similar to 2, [Pt2H2(mu-(PBu2)-Bu-t)(2)(PEt3)(2)] (4), is obtained by the reaction of (t)-Bu2PH with Pt(PEt3)(3). Isolated complexes 2 and 3 cleanly react with Ph2PH to form 1, indicating that the reaction of Ph2PH with Pt(PEt3)(3), giving 1, involves these complexes as the intermediates. Complex 3 contains a triangular Pt-3 core with Pt-Pt bonds in the range 2.9784(4)-2.9983(3) Angstrom, as shown by X-ray crystallography. The H-1 NMR spectrum of 3 exhibits the hydrido signal at delta - 7.98 accompanied by splitting due to H-P and H-Pt coupling. Complex 3 reacts with Ph3SiH and Ph2SiH2 to give silylplatinum complexes [Pt-3(SiHn+1Ph4-n)(mu-PPh2)(3)(PEt3)(2)] (5, n = 1; 6, n = 2). Cationic triangular complexes [Pt-3(mu-PPh2)(3)(PEt3)(3)]I-+(-) (7) and [Pt-3(mu-PPh2)(3)(PEt3)(3)](+)[B4O4Ar4(OH)](-) (8, Ar = C6H4Me-4; 9, Ar = C6H4F-4; 10, Ar = C(6)H(4)CF(3-)4) are obtained from the reactions of complex 3 with MeI and with ArB(OH)(2), respectively.

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  • Synthesis and structural characterization of the first unsymmetrical diarylpalladium complex trans-Pd(C6F5)(2,4,6-C6F3H2)(PEt3)(2), derived from transmetallation between 2,4,6-trifluorophenylboronic acid and trans-Pd(C6F5)I(PEt3)(2)

    Y Nishihara, H Onodera, K Osakada

    CHEMICAL COMMUNICATIONS   ( 2 )   192 - 193   2004.1

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    The reactions of 2,4,6-trifluorophenylboronic acid with aryl(iodo)palladium(II) complexes, trans-Pd(C6F5)I(PR3)(2)(PR3 = PEt3, PMe2Ph, PMePh2) in the presence of Ag2O afforded transPd(C6F5)(2,4,6-C6F3H2)(PR3)(2) which are stabilized by fluorine atoms in the ortho positions.

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  • New stable complexes of Au(III) with biuret: X-ray structure of cis-[Au(Biu)Br-2]PPh4 and Ab initio investigation of cis-[Au(Biu)X-2](-)

    N Mintcheva, M Mitewa, Enchev, V, Y Nishihara

    JOURNAL OF COORDINATION CHEMISTRY   56 ( 4 )   299 - 305   2003.3

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    Two anionic complexes of Au(III) with the bioligand biuret, cis-[Au(Biu)X-2](-) (BiuH(2)=biuret, X=Cl, Br), have been synthesized and characterized. The molecular structure of cis-[Au(Biu)Br-2]PPh4 has been determined by X-ray diffraction analysis. The complex anion has square-planar geometry with one deprotonated biuret dianion coordinated bidentately to the metal center via the terminal amino nitrogen atoms and two bromide ions in cis positions. There are no significant intermolecular Au-Au interactions in the solid state. Ab initio calculations of the geometric structure at different computational levels for biuret and both anionic complexes as well an IR study of the structures obtained are performed.

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  • Platinum complex-catalyzed hydrosilylation and isomerization of methylenecyclopropane derivatives. Effect of structures of the substrate and catalyst

    M Itazaki, Y Nishihara, K Osakada

    JOURNAL OF ORGANIC CHEMISTRY   67 ( 20 )   6889 - 6895   2002.10

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    PtI2(PPh3)(2) catalyzes hydrosilylation of 2,2-diphenyl-1-methylenecyclopropane with HSiEt3, HSiPh3, HSiEt2Ph, HSiPhCl2, and HSiCl3 under solvent-free conditions at 140 degreesC to produce the silyl compounds with a (2,2-diphenyleyclopropyl)methyl substituent in moderate to high yields without ring-opening of the substrate. PtI2(PPh3)(2) is converted by the reaction into PtH(I)(PPh3)(2), which also catalyzes the hydrosilylation of the methylenecyclopropanes. The reaction of 2-phenyl-1-methylenecyclopropane, 2-methyl-2-phenyl-1-methylenecyclopropane, 2,2-diphenethyl-1-methyl-enecyclopropane, and alkylidenecyclopropanes with HSiEt3 catalyzed by PtI2(PPh3)(2) causes addition of hydrosilane to the substrate accompanied by ring-opening. 2,2-Diphenyl-1-methylenecyclopropane undergoes ring-opening isomerization in the presence of HSi(OEt)Me-2 and Pt(PEt3)(3) catalyst to give 1,1-diphenyl-1,3-butadiene. The pathways for the hydrosilylation and the isomerization are discussed.

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  • Tetraarylpentaborates, [B5O6Ar4](-) (Ar = C6H4OMe-4, C6H3Me2-2,6): Their formation from the reaction of arylboronic acids with an aryloxorhodium complex, structure, and chemical properties

    Y Nishihara, K Nara, K Osakada

    INORGANIC CHEMISTRY   41 ( 16 )   4090 - 4092   2002.8

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    The reactions of (4-methoxyphenyl)boronic acid (1a) and of (2,6-dimethylphenyl)boronic acid (1 b) with (PMe3)(3)Rh-(OC6H4Me-4) (2) in a 5:1 molar ratio result in the formation of cationic rhodium complexes with new tetraarylpentaborates [Rh(PMe3)(4)](+)[B5O6Ar4](3a, Ar = C6H4OMe-4; 3b, Ar = C6H3Me2-2,6). The characterization of 3a is as follows: orthorhombic space group P2(1)2(1)2(1), a = 14.7600(5) Angstrom, b =17.1675(5) Angstrom, c = 19.8654(5) Angstrom; V = 5033.7(3) Angstrom(3); Z = 4. The characterization of 3b is as follows: orthorhombic space group Pnma, a = 23.704(6) Angstrom, b = 17.254(8) Angstrom, c = 13.304(2) Angstrom; V = 5441(2) Angstrom(3); Z = 4. An intermediate complex, [Rh(PMe3)(4)](+)[Ph3B3O3(OC6H4Me-4)](-) (4), was isolated from the reaction of phenylboroxine, (PhBO)(3), with 2. The tetraarylpentaborates smoothly undergo hydrolysis to give [Rh(PMe3)(4)](+)[B5O6(OH)(4)](-) (5).

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  • Platinum complex-catalyzed hydrosilylation of 2,2-diaryl-1-methylenecyclopropane affording (silylmethyl)cyclopropane

    Y Nishihara, M Itazaki, K Osakada

    TETRAHEDRON LETTERS   43 ( 11 )   2059 - 2061   2002.3

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    PtI2(PPh3)(2)-catalyzed hydrosilylation of 2.2-diphenyl-1-methylenecyclopropane with HSiEt3 forms (2,2-diphenylcyclopropyl)methyl(triethyl)silane in 87% yield as a sole product. This highly selective addition of Si-H bond converts 2,2-diaryl-1-methylenecyclopropane into its silylated derivative without ring-opening. (C) 2002 Elsevier Science Ltd. All rights reserved.

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  • Structure and properties of halogeno(hydrido) (triorganosilyl)rhodium(III) complexes, RhX(H) ((SiRnR3-n2)-R-1)(PPh3)(2) (X = Cl, I; R-1 = OSiMe3, OEt, R-2 = Me). Influence of the alkoxy groups and halo ligand on stability and reactivity of the complexes

    Y Nishihara, M Takemura, K Osakada

    ORGANOMETALLICS   21 ( 5 )   825 - 831   2002.3

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    Silylrhodium(III) complexes RhX(H)((SiRnR3-n2)-R-1)(PPh3)(2) (1: X = I, R-1 = OSiMe3, R-2 = Me, n = 1; 2: X= I, R-1 = OEt,n = 3; 3: X = I, R-1 = OEt, R-2 = Me, n = 2; 4: X=I, R-1 = OEt, R-2 = Me, n = 1; 5: X= Cl, R-1 = OSiMe3, R-2 = Me, n = 1; 6: X = Cl, R-1 = OEt, n = 3; 7: X = Cl, RI = OEt, R2 = Me, n = 2; 8: X = Cl, R-1 = OEt, R-2 = Me, n = 1) were prepared by oxidative addition of (HSiRnR3-n2)-R-1 to RhX(PPh3)(3) and characterized by means of NMR (H-1, C-13{H-1}, P-31{H-1}, and Si-29{H-1}) and IR spectroscopy as well as elemental analyses. X-ray crystallography of 1, 2, and 6 showed a distorted square-pyramidal coordination around the Rh center that is bonded to the silyl ligand at the apical position and to halo and hydrido ligands in trans positions in the basal plane. The Rh-Si bonds in 2 and 6 are the shortest among Rh-Si bonds of the silylrhodium complexes reported to date. Si-29{H-1} NMR spectra of 1-8 show that the J(RhSi) value increases with an increase in the number of alkoxy substituents on the Si atom. Complex 2 reacted with HSiMe2(OSiMe3), HSi(OEt)(2)Me, and HSi(OEt)Me-2, respectively, to cause exchange of the silyl group between the Rh complex and the organosilane, forming an equilibrium mixture. Complexes 5-8 undergo thermally induced coupling of their chloro and triorganosilyl ligands at 60 degreesC to liberate the respective chloro(triorgano)silane. The reaction obeys first-order kinetics in the Rh complex with the observed rate constants in the order 5 congruent to 8 &gt; 7 &gt; 6. The OEt groups at the Si retard the coupling of chloro and triorganosilyl ligands significantly. Formation of ISiMe2(OEt)(2) from 4 takes place at a slightly slower rate than the reaction of 6, while complexes 2 and 3 do not undergo coupling of their iodo and silyl ligands at 60 degreesC.

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  • Isomerization of (Z)-alkenylsilanes to (E)-isomers with hydrosilane and RhI(PPh3)(3)

    A Mori, E Takahisa, Y Nishihara, T Hiyama

    CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE   79 ( 11 )   1522 - 1524   2001.11

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    Isomerization of (E)-2-phenylethenylsilanes to the (Z)-isomers is found to easily take place at 60 degreesC within 1 h using 20-100 mol% of a hydrosilane and 0.1 mol% of RhI(PPh3)(3) and is understood in terms of insertion of alkenylsilanes to hydridorhodium followed by beta -hydride elimination.

    DOI: 10.1139/cjc-79-11-1522

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  • Homo-coupling polycondensation of bis(alkynylsilane)s mediated by copper(I) chloride: A new synthesis of poly(arylenebutadiynylene)s

    Y Nishihara, T Kato, J Ando, A Mori, T Hiyama

    CHEMISTRY LETTERS   ( 10 )   950 - 951   2001.10

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    Homo-coupling polycondensation of aromatic compounds bearing two (trimethylsilyl)ethynyl groups mediated by copper(I) chloride in DMF gives conjugated poly(arylenebutadiynylene)s in up to 94% yield with molecular weight of 4000-8900 (M-w/M-n = 1.78-2.09).

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  • Preparation and reactions of monocyclic bis(cyclopentadienyl)titanacyclopentenes and -pentadienes

    K Sato, Y Nishihara, SQ Huo, ZF Xi, T Takahashi

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   633 ( 1-2 )   18 - 26   2001.9

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    A combination of CP2TiCl2-2EtMgBr was found to be very effective for the formation of monocyclic titanacyclopentenes in excellent yields. On the other hand, a combination of Cp2TiCl2-2n-BuLi was used for intermolecular coupling of two alkynes to form titanacyclopentadienes in good to excellent yields. A reaction temperature range from -10 to -30 degreesC was critical for the success of the combinations. Reactions of these in situ-prepared titanacycles show interesting similarities to or differences from their zirconacycle analogs. (C) 2001 Published by Elsevier Science BN.

    DOI: 10.1016/S0022-328X(01)01072-5

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  • Reactions of HOSiMe2Ar with PtPPh3 complexes leading to Si-C bond activation or formation of a siloxoplatinum complex

    N Mintcheva, Y Nishihara, A Mori, K Osakada

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   629 ( 1-2 )   61 - 67   2001.6

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    PtI2(PPh3)(2) reacts with HOSiMe2(C6H4CF3-4) at 60 degreesC in the presence of AgBF4 to give a mixture of trans-PtI(C6H4CF3-4)(PPh3)(2) (1) and [Pt-2(mu -I)(2)(PPh3)(4)](BF4)(2) (2). Each of the complexes is isolated and characterized by X-ray crystallography and/or NMR spectroscopy. The P-31{H-1}-NMR study of the reaction of AgBF4 with PtI2(PPh3)(2) in acetone-d(6) revealed the formation of trans-[PtI(PPh3)(2)(acetone)]BF4 (3) although isolation of the cationic complex was not feasible due to its facile conversion to 2. Addition of HOSiMe2(C6H4CF3-4) and Ag2O to a toluene Solution of trans-PtI(Ph)(PPh3)(2) causes replacement of the iodo ligand with the siloxo group to afford trans-[Pt(Ph) {OSiMe2(C6H4CF3-4)} (PPh3)(4)] (4). Crystallographic results of 4 show the coordination of the phenyl, siloxo, and PPh3 ligands to the square-planar Pt center with a large Pt-O-Si angle. Complex 4 does not decompose below 60 degreesC in a toluene solution, but reacts with CH2Cl2 and CHCl3 at room temperature to form trans-Pt-Cl(Ph)(PPh3)(2) (5). (C) 2001 Elsevier Science B.V. All rights reserved.

    DOI: 10.1016/S0022-328X(01)00796-3

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  • Hydrido-Rhodium(I) and -Iridium(I) complex promoted ring-opening isomerization of unsymmetrically substituted methylenecyclopropanes into 1,3-dienes. Structures of intermediates and reaction pathways

    Y Nishihara, C Yoda, K Osakada

    ORGANOMETALLICS   20 ( 11 )   2124 - 2126   2001.5

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    2-Phenyl-1-methylenecyclopropane and 2,2-diphenyl-1-methylenecyclopropane react with MH(CO)(PPh3)(3) (M = Rh, Ir) to produce 1,3-dienes or the intermediate Rh and Ir complexes having a 3-butenyl ligand, depending on the conditions. The structures and chemical properties of the obtained complexes suggest plausible pathways for the ring-opening isomerization of the methylenecyclopropanes to the corresponding dienes.

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  • Palladium-catalyzed cross-coupling polycondensation of bisalkynes with dihaloarenes activated by tetrabutylammonium hydroxide or silver(I) oxide

    A Mori, T Kondo, T Kato, Y Nishihara

    CHEMISTRY LETTERS   ( 4 )   286 - 287   2001.4

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    The palladium(O)-catalyzed polycondensation of bis-trimethylsilylethynylated compounds with diiodoarenes to give the polymers bearing arylene-ethynylene moieties is carried out by the use of silver(I) oxide as an activator. Polycondensation of bifunctional terminal alkynes and aryl halides is also accomplished by the palladium-catalyzed cross coupling in the presence of tetrabutylammonium hydroxide (TBAOH), tetrabutylammonium fluoride (TBAF), or silver(I) oxide.

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  • Si-C bond activation of ArMe2SiOH promoted by a bromoplatinum(II) complex and Ag2O. Aryl group transfer from silicon to platinum

    N Mintcheva, Y Nishihara, M Tanabe, K Hirabayashi, A Mori, K Osakada

    ORGANOMETALLICS   20 ( 6 )   1243 - 1246   2001.3

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    [PtBr(PEt3)(3)]BF4 (1) reacts with art excess of dimetliyl{4-(trifluoromethyl)phenyl}silanol in the presence of Ag2O and 4 Angstrom molecular sieves at 60 OC to afford trans-Pt(C6H4CF3-4)(2)(PEt3)(2) (2) The reaction without molecular sieves and that with addition of a smalE amount of water give a mixture of 2 and [Pt-2(mu -OH)(2)-(PEt3)(4)](BF4)(2). The organic products of the reaction are composed of ArSiMe2-O-(SiMe2-O)(n)-SiMe2Ar (Ar = C6H4 CF3-4, n = 0, 1, 2) a nd cyclooligodimethylsiloxanes in lesser amounts. The obtained complexes were characterized by NMR spectroscopy and X-ray crystallography.

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  • Reaction of alkynylsilanes with CuCl in polar solvents leading to alkynyl group transfer from Si to Cu

    Y Nishihara, M Takemura, A Mori, K Osakada

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   620 ( 1-2 )   282 - 286   2001.2

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    The reaction of 1-phenyl-2-trimethylsilylethyne with CuCl at 80-100 degreesC in N,N-dimethylformamide (DMF) or N,N-dimethylimidazolidinone (DMI) yielded the alkynylcopper species[Cu2Cl(C drop CPh)(n)] (1) in 56-63% yields. Heating 1 at 80 degreesC under aerobic conditions gave 1,4-diphenyl-1,3-butadiyne in 82% yield via an oxidative coupling of the phenylethynyl ligands. (C) 2001 Elsevier Science B.V. All rights reserved.

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  • Non-Sonogashira-type palladium-catalyzed coupling reactions of terminal alkynes assisted by silver(I) oxide or tetrabutylammonium fluoride

    A Mori, J Kawashima, T Shimada, M Suguro, K Hirabayashi, Y Nishihara

    ORGANIC LETTERS   2 ( 19 )   2935 - 2937   2000.9

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    [GRAPHICS]
    Palladium-catalyzed reaction of aryl and alkenyl halides with terminal alkynes in the presence of silver(I) oxide as an activator furnishes various arylated or alkenylated alkynes in good to excellent yields, The similar coupling reaction is also found to proceed using tetrabutylammonium fluoride (TBAF) or tetrabutylammonium hydroxide (TBAOH) as an activator.

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  • Palladium-catalyzed cross-coupling of silanols, silanediols, and silanetriols promoted by silver(I) oxide

    E Hirabayashi, A Mori, J Kawashima, M Suguro, Y Nishihara, T Hiyama

    JOURNAL OF ORGANIC CHEMISTRY   65 ( 17 )   5342 - 5349   2000.8

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    Palladium-catalyzed cross-coupling of aryl- or alkenylsilanols, silanediols, and silanetriols with a variety of iodoarenes by the catalysis of palladium(0) and in the presence of silver(I) oxide furnished the coupling products in good to excellent yields. The reactions of silanediols or silanetriols under similar conditions proceeded much faster than those of silanols to afford the corresponding coupling products in excellent yields within shorter reaction periods (5-12 h). The measurement of the X-ras diffraction (XRD) pattern of the silver residue after the reaction revealed that silver(I) oxide was converted to silver(I) iodide.

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  • Novel carbon-carbon bond formation through Mizoroki-Heck type reaction of silanols and organotin compounds

    K Hirabayashi, J Ando, J Kawashima, Y Nishihara, A Mori, T Hiyama

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   73 ( 6 )   1409 - 1417   2000.6

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    The reaction of dimethyl(phenyl)silanol with butyl acrylate in the presence of a stoichiometric amount of Pd(OAc)(2) or by a combined use of 0.1 molar amount of Pd(OAc)(2) and Cu(OAc)(2)/LiOAc (molar ratio 3/2) gave butyl cinnamate in 76% or 57% yield, respectively. The similar reaction with tributyl(phenyl)tin also proceeded in 77% yield. The organotin compound was shown to react faster than the silanol, although the tin reagent sometimes induced undesirable homo-coupling, while the reaction with silanol did not give such by-product.

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  • A novel cross-coupling polycondensation of alkynylsilanes with aryl triflates catalyzed by CuCl/Pd(PPh3)(4)

    Y Nishihara, J Ando, T Kato, A Mori, T Hiyama

    MACROMOLECULES   33 ( 8 )   2779 - 2781   2000.4

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    DOI: 10.1021/ma9908301

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  • Home-coupling reactions of alkenyl- and arylfluorosilanes mediated by a copper(I) salt

    Y Nishihara, K Ikegashira, F Toriyama, A Mori, T Hiyama

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   73 ( 4 )   985 - 990   2000.4

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    Home-coupling reactions of an alkenyl- or arylsilane readily occur with a copper(I) salt in an aprotic polar solvent such as N, N-dimethylformamide or dimethyl sulfoxide under an aerobic condition to give the corresponding conjugated dienes or biaryls, respectively. Optimization of a copper salt and a solvent for the home-coupling reaction is discussed. The formation of the organocopper intermediates is evidenced by trapping experiments with iodine and by a conjugate addition to methyl vinyl ketone.

    DOI: 10.1246/bcsj.73.985

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  • Coupling reactions of alkynylsilanes mediated by a Cu(I) salt: Novel syntheses of conjugate diynes and disubstituted ethynes

    Y Nishihara, K Ikegashira, K Hirabayashi, J Ando, A Mori, T Hiyama

    JOURNAL OF ORGANIC CHEMISTRY   65 ( 6 )   1780 - 1787   2000.3

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    Reaction of 1-trimethylsilylalkyne with copper(I) chloride in a polar solvent, DMF, at 60 OC under an aerobic conditions smoothly undergoes home-coupling to give the corresponding symmetrical 1,3-butadiynes in 70-99% yields. In addition, (arylethynyl)trimethylsilanes are found to couple with aryl triflates and chlorides in the presence of Cu(I)/Pd(0) (10 mol %/5 or 10 mol %) cocatalyst system to give the corresponding diarylethynes in 49-99% yields. The cross-coupling reaction is applied to a one-pot synthesis of the corresponding unsymmetrical diarylethynes from (trimethylsilyl)ethyne via sequential Sonogashira-Hagihara and the present cross-coupling reactions using two different aryl triflates. The reactions of (arylethynyl)trimethylsilanes with aryl(chloro)ethynes in the presence of 10 mol % of CuCl also yield the corresponding unsymmetrical 1,3-butadiynes in 43-97% yields.

    DOI: 10.1021/jo991686k

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  • Substituent effect of 3,3,3-trifluoropropyl group on organic silanols. Palladium-mediated Mizoroki-Heck type and cross-coupling reactions

    K Hirabayashi, T Kondo, F Toriyama, Y Nishihara, A Mori

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   73 ( 3 )   749 - 750   2000.3

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    The Mizoroki-Heck type reaction of methyl(phenyl)(3,3,3-trifluoropropyl)silanol (1a) with ethyl acrylate in the presence of Pd(OAc)(2) (10 mol%) and Cu(OAc)(2)/LiOAc gave ethyl cinnamate in 70% yield. The palladium-catalyzed cross-coupling of la with 4-iodomethoxybenzene in the presence of Ag2O also afforded 4-methoxybiphenyl in 51% yield.

    DOI: 10.1246/bcsj.73.749

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  • Stereodivergent hydrosilylation of 1-alkynes catalyzed by RhI(PPh3)(3) leading to (E)- and (Z)-alkenylsilanes and the application to polymer synthesis

    A Mori, E Takahisa, H Kajiro, Y Nishihara, T Hiyama

    POLYHEDRON   19 ( 5 )   567 - 568   2000.3

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    Hydrosilylation of 1-alkynes catalyzed by RhI(PPh3)(3) gives (E)- and (Z)-alkenylsilanes in a stereodivergent manner by switching the reaction conditions and the order of the addition of the reagents. The reaction is also applied to the synthesis of silicon-containing polymers with (E) and (Z) main-chain structures via polyaddition. (C) 2000 Elsevier Science Ltd All rights reserved.

    DOI: 10.1016/S0277-5387(99)00409-X

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  • Regio- and stereocontrolled hydrosilylation polyaddition catalyzed by RhI(PPh3)(3). Syntheses of polymers containing (E)- or (Z)-alkenylsilane moieties

    A Mori, E Takahisa, H Kajiro, Y Nishihara, T Hiyama

    MACROMOLECULES   33 ( 4 )   1115 - 1116   2000.2

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    DOI: 10.1021/ma9913360

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  • Preparation and characterization of bis(cyclopentadienyl)zirconium(II) complexes with a tethered olefin-phosphine ligand

    A Yamazaki, Y Nishihara, K Nakajima, R Hara, T Takahashi

    ORGANOMETALLICS   18 ( 16 )   3105 - 3108   1999.8

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    Unprecedented zirconium(II) complexes bearing tethered olefin-phosphine ligands were synthesized and characterized. The molecular structures of the newly synthesized complexes (eta(5)-1,2-Me2C5H3)(2)Zr(CH2=CHCH2CH2PPh2) (1c) and Cp2Zr(CH2=CHCH2CH2CH2PPh2) (2a) were determined by single-crystal X-ray diffraction methods. The stability and reactivity of the series of complexes Cp2Zr{CH2=CH(CH2)(n)PR2} (n = 2, 3; R = Et, Ph) were examined. The complex 2a showed simultaneously both sufficient stability and high reactivity.

    DOI: 10.1021/om990103u

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  • Palladium-catalyzed carbon-carbon bond-forming reactions of silanols. Reviewed

    K Hirabayashi, D Kawashima, Y Nishihara, A Mori, T Hiyama

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   218   U101 - U101   1999.8

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  • Homo- and cross-coupling reactions of alkynylsilanes mediated by a copper(I) salt. Reviewed

    Y Nishihara, K Ikegashira, K Hirabayashi, A Mori, T Hiyama

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   218   U195 - U195   1999.8

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  • Synthesis and optical resolution of novel chiral silanols

    A Mori, F Toriyama, H Kajiro, K Hirabayashi, Y Nishihara, T Hiyama

    CHEMISTRY LETTERS   ( 7 )   549 - 550   1999.7

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    Silanols bearing an asymmetric center on silicon, methyl(2-phenylethenyl) (3,3,3-trifluoropropyl)silanol and methyl(phenyl)(vinyl)silanol are synthesized by alkylative cleavages of cyclic siloxanes with an organolithium. Optical resolution of their enantiomers is performed by HPLC with a chiral stationary phase column. Optical characters of thus separated enantiomers are also examined.

    DOI: 10.1246/cl.1999.549

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  • A new transformation of silanols. Palladium-catalyzed cross-coupling with organic halides in the presence of silver(I) oxide

    K Hirabayashi, J Kawashima, Y Nishihara, A Mori, T Hiyama

    ORGANIC LETTERS   1 ( 2 )   299 - 301   1999.7

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    The reactions of aryl- and alkenylsilanols with organic halides are found to proceed in a catalyst system of 5 mol % of Pd(PPh3)(4) and Ag2O (1 equiv) to give the corresponding coupling products in up to 84% yield.

    DOI: 10.1021/ol990614c

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  • A unique chelating effect of Sc(OTf)(3) to organofluorine compounds

    H Kajiro, A Mori, Y Nishihara, T Hiyama

    CHEMISTRY LETTERS   ( 6 )   459 - 460   1999.6

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    The scandium trifluoromethanesulfonate-catalyzed cleavage of acetate bearing two or three fluorine atoms at a position beta to an acetoxy group proceeds exceptionally rapidly. The high efficiency of the hydrolysis is caused by a chelating effect of scandium with the fluorine atoms and an acetate moiety.

    DOI: 10.1246/cl.1999.459

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  • Conjugate reduction of alpha,beta-unsaturated ketones with hydrosilane mediated by copper(I) salt

    A Mori, A Fujita, H Kajiro, Y Nishihara, T Hiyama

    TETRAHEDRON   55 ( 15 )   4573 - 4582   1999.4

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    Reduction of several alpha,beta-unsaturated ketones with dimethylphenylsilane and 10-100 mol% of CuF(PPh3)(3). 2EtOH or CuCl/PPh3/Bu4NF proceeds in a 1,4-selective manner to give the corresponding saturated ketones in up to &gt;99% yield. (C) 1999 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0040-4020(99)00141-6

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  • A coupling reaction of aryltributyltin with olefins mediated by palladium(II) acetate

    K Hirabayashi, J Ando, Y Nishihara, A Mori, T Hiyama

    SYNLETT   ( 1 )   99 - 101   1999.1

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    Phenytributyltin is found to react with butyl acrylate in the presence of Pd(OAc)(2) (10 mol%), Cu(OAc)(2) (3 mel), and LiO-Ac (2 mel) in DMF to afford butyl 3-phenylpropenoate in 77% yield. Methyl vinyl ketone, acrolein, acrylonitrile, and styrene are also applicable to this reaction as a substrate.

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  • Copper(I)-catalyzed cross-coupling reaction of alkynylsilanes with 1-chloroalkynes Reviewed

    Nishihara Y, Ikegashira K, Mori A, Hiyama T

    Tetrahedron Letters   39 ( 23 )   4075 - 4078   1998

  • RhCl(PPh3)(3)/NaI catalyst system for hydrosilylation of 1-alkynes: Stereodivergent syntheses of E- and Z-alkenylsilanes with heteroatom substituents on silicon Reviewed

    Mori A, Takahisa E, Kajiro H, Hirabayashi K, Nishihara Y, Hiyama T

    Chemistry Letters   1998 ( 5 )   443 - 444   1998

  • A novel C-C bond forming reaction of aryl- and alkenylsilanols. A halogen-free Mizoroki-Heck type reaction Reviewed

    Hirabayashi K, Nishihara Y, Mori A, Hiyama T

    Tetrahedron Letters   39 ( 43 )   7893 - 7896   1998

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  • A facile preparation and cyclopropanation of 1-alkenylsilanols Reviewed

    Hirabayashi K, Takahisa E, Nishihara Y, Mori A, Hiyama T

    Bulletin of the Chemical Society of Japan   71 ( 10 )   2409 - 2417   1998

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    Alkenylsilanols are prepared by the reaction of hexamethyltrisiloxane (D3) with alkenyllithiums or alternatively by the reaction of cyclic siloxanes substituted by an alkenyl group with organolithiums and transformed to the corresponding cyclopropylsilanols using diiodomethane and diethylzinc. Lithium alkenylsilanolates, primary products of the preparation, also undergo cyclopropanation. As in the case of allylic alcohols, the silanol functionality is found to enhance the rate of cyclopropanation compared with that of alkenyltrialkylsilane or alkoxydialkylsilane. The obtained cyclopropylsilanols are further converted into the corresponding cyclopropanols by the Tamao oxidation.

    DOI: 10.1246/bcsj.71.2409

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  • Preparation and reactions of Cp2HfRCl, Cp2HfRR′ and hafnacyclopent-2-enes Reviewed

    Yasushi Nishihara, Toyohisa Ishida, Shouquan Huo, Tamotsu Takahashi

    Journal of Organometallic Chemistry   547 ( 2 )   209 - 216   1997.12

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    Reaction of Cp2HfCl2 with R3Al (R = Et, n-Pr, or n-Bu) in hexane selectively produced monoalkylhafnocene complexes, Cp2HfRCl (1), in high yields. Cp2HfMeCl (1a) was prepared by the reaction of oxo-bridged hafnocene complex (Cp2HfCl)2(μ-O) with Me3Al. The treatment of 1 with alkylating reagents such as R′Li or EtMgBr afforded unsymmetrical dialkylhafnocene complexes Cp2HfRR′ (3) in good to excellent yields. The kinetic study of thermolysis of Cp2HfEtR (R = Me, Et, n-Bu, sec-Bu, t-Bu or Ph) suggested that decomposition of Cp2HfEt(sec-Bu) was much faster than the others. Cp2Hf(sec-Bu)2 (2e) can be used as a good precursor of Cp2Hf(II) species. Hafnacyclopent-2-enes (4) were prepared in good yields by the reaction of Cp2HfEt2 (2b) with alkynes. © 1997 Elsevier Science S.A.

    DOI: 10.1016/S0022-328X(97)00375-6

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  • Highly regio- and diastereo-selective carbon-carbon bond formation reaction of unsymmetrical zirconacyclopentanes using copper salt Reviewed

    T Takahashi, Y Nishihara, R Hara, SQ Huo, M Kotora

    CHEMICAL COMMUNICATIONS   ( 17 )   1599 - 1600   1997.9

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    Reaction of unsymmetrical zirconacyclopentanes with allyl chloride or benzoyl chloride in the presence of copper chloride gave allylated or benzoylated products with high regio- and diastereo-selectivities.

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  • Convenient preparative method of alpha,beta-disubstituted cyclopentenone by zirconium promoted intermolecular coupling of an alkyne, EtMgBr (or ethylene) and CO Reviewed

    T Takahashi, ZF Xi, Y Nishihara, SQ Huo, K Kasai, K Aoyagi, Denisov, V, E Negishi

    TETRAHEDRON   53 ( 27 )   9123 - 9134   1997.7

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    Treatment of Cp2ZrCl2 with 2 equiv of EtMgBr in THF, followed by addition of an internal alkyne and subsequent treatment with CO/I-2 gave alpha,beta-disubstituted cyclopentenone in good to high yields. When a conjugated enyne was used as an alkyne component, alpha-alkenyl cyclopentenone was selectively formed in 80-89% yields. In the case of 4,6-decadiyne, alpha-alkynylcyclopentenone was formed in 88% yield. Bridged alkynes such as 1,4-dihexynytbenzene afforded alpha alpha'-bridged cyclopentenone compounds in good yields. (C) 1997 Elsevier Science Ltd.

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  • Coupling reaction of alkenylzirconocenes with aryl or alkenyl iodides in the presence of CuCl/Pd(PPh(3))(4) Reviewed

    R Hara, Y Nishihara, PD Landre, T Takahashi

    TETRAHEDRON LETTERS   38 ( 3 )   447 - 450   1997.1

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    Trisubstituted alkenylalkoxyzirconocenes which have been prepared from carbozirconation reactions of internal alkynes via zirconacyclopentenes reacted with aryl or alkenyl iodides in the presence of CuCl and a catalytic amount of Pd(PPh(3))(4) to give coupling products. Copyright (C) 1996 Elsevier Science Ltd

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  • Cu(I)/Pd(0)-catalyzed cross-coupling reaction of alkynylsilanes with aryl or alkenyl triflates: "Sila"-Sonogashira-Hagihara coupling Reviewed

    Nishihara Y, Ikegashira K, Mori A, Hiyama T

    Chemistry Letters   1997 ( 12 )   1233 - 1234   1997

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    Alkynylsilanes reacted with aryl or alkenyl triflates in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuCl in DMF to give the corresponding cross-coupling, namely "sila"-Sonogashira-Hagihara coupling, products in good to excellent yields. The present reaction is highly effective for one-pot synthesis of unsymmetrical diarylacetylenes.

    DOI: 10.1246/cl.1997.1233

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  • Copper(I) salt promoted homo-coupling reaction of organosilanes Reviewed

    Ikegashira K, Nishihara Y, Hirabayashi K, Mori A, Hiyama T

    Chemical Communications   ( 11 )   1039 - 1040   1997

  • TBAHF(2) and TBAH(2)F(3) as activating agents of organosilanes Reviewed

    Mori A, Fujita A, Ikegashira K, Nishihara Y, Hiyama T

    Synlett   ( 6 )   693 - 694   1997

  • Copper(I) salt mediated 1,4-reduction of alpha,beta-unsaturated ketones using hydrosilanes Reviewed

    Mori A, Fujita A, Nishihara Y, Hiyama T

    Chemical Communications   1997 ( 22 )   2159 - 2160   1997

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    DOI: 10.1039/a706032g

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  • Zirconocene catalyzed dehalogenation of aromatic halides by alkylmagnesium reagents Reviewed

    R Hara, WH Sun, Y Nishihara, T Takahashi

    CHEMISTRY LETTERS   ( 12 )   1251 - 1252   1997

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    When aromatic halides were treated with alkylmagnesium reagents (which have beta-hydrogens) and a catalytic amount of zirconocene dichloride, dehalogenation proceeded smoothly in high yields. The stoichiometric dehalogenation using dialkylzirconocenes also proceeded with high selectivities.

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  • Highly selective monofunctionalization of zirconacyclopentanes and dialkylzirconocene complexes Reviewed

    Y Nishihara, K Aoyagi, R Hara, N Suzuki, T Takahashi

    INORGANICA CHIMICA ACTA   252 ( 1-2 )   91 - 99   1996.11

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    Selective monofunctionalization was investigated for symmetrical zirconacyclopentanes or symmetrical dialkylzirconocenes. Reaction of zirconacyclopentanes, which were prepared by intermolecular coupling of two alkenes, or intramolecular cyclization of dienes, trienes or tetraenes on zirconium, with PPh(2)Cl or SnR(3)Cl (R = Me, Ph) gave monofunctionalized products in good to high yields with high selectivities. Even in the presence of 2 equiv, of PPh(2)Cl or SnR(3)Cl, only one Zr-carbon bond reacted. Treatment of zirconacycropentanes with methanol yielded monoprotonated complexes. Subsequent addition of halogen such as Br-2 and I-2 to these monoprotonated complexes gave highly selective monohalogenated products. Similar monoprotonation reactions proceeded for dialkylzirconocene or -hafnocene complexes. Reaction of Cp(2)MR(2) (M = Zr or Hf, R = alkyl or aryl) with alcohols afforded alkylalkoxyzirconocene or -hafnocene complexes, Cp(2)MR(OR') (M = Zr or Hf, R' = alkyl or aryl) in high yields with high selectivities. High selectivity of monofunctionalization using PPh(2)Cl, SnR(3)Cl or alcohols can be attributed to the different reactivities between monoalkylzirconocenes which are monofunctionalized products and zirconacyclopentanes or dialkylzirconocenes.

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  • Copper-mediated coupling of zirconacyclopentadienes with dihalo aromatic compounds. Formation of fused aromatic rings Reviewed

    T Takahashi, R Hara, Y Nishihara, M Kotora

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   118 ( 21 )   5154 - 5155   1996.5

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  • PRACTICAL AND SELECTIVE METHOD FOR PREPARATION OF CP(2)HFRCL AND CP(2)HFRR' Reviewed

    T TAKAHASHI, Y NISHIHARA, T ISHIDA

    CHEMISTRY LETTERS   ( 2 )   159 - 160   1995.2

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    Practical method for preparation of Cp(2)HfRCl and Cp(2)HfRR' has been investigated. Mono(alkyl)hafnocene chloride complexes were selectively prepared by the following methods; (i) a reaction of Cp(2)HfR(OMe) with MeCOCl and (ii) a reaction of Cp(2)HfCl(2) with an excess of R(3)Al. Treatment of Cp(2)HfRCl with R'Al-3 led to an alkyl exchange reaction to form Cp(2)HfR'Cl. Mono(alkyl)hafnocene complexes prepared by (ii) reacted with one equiv of R'Li to give Cp(2)HfRR' (R not equal R') with a high selectivity.

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  • Oxidative Addition of 2-Haloalkene to Zirconocene Reviewed

    Tamotsu Takahashi, Martin Kotora, Reinald Fischer, Yasushi Nishihara, Kiyohiko Nakajima, Tamotsu Takahashi

    Journal of the American Chemical Society   117 ( 44 )   11039 - 11040   1995

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    DOI: 10.1021/ja00149a040

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  • ジルコニウム錯体 ZrN4S2

    西原康師( Role: Joint author)

    朝倉書店  2019 

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  • チタン錯体 TiC2NP

    西原康師( Role: Joint author)

    2019 

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  • チタン錯体 TiB3C2N2O

    西原康師( Role: Joint author)

    朝倉書店  2019 

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  • チタン錯体 Ti4O16

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    朝倉書店  2019 

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  • チタン錯体 Ti2O7

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    朝倉書店  2019 

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  • ジルコニウム錯体 ZrC10Cl2

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    朝倉書店  2019 

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  • ジルコニウム錯体 ZrC3NI2

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    朝倉書店  2019 

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  • チタン錯体 TiPd2H2O6P8

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    朝倉書店  2019 

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  • チタン錯体 Ti2N9Cl

    西原康師( Role: Joint author)

    朝倉書店  2019 

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  • 有機ジルコニウム化合物 (19.2.3)

    丸善出版  2015 

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  • ハートウィグ 有機遷移金属化学(上)

    東京化学同人  2014  ( ISBN:4807908502

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  • Applied Cross-Coupling Reactions (Lecture Notes in Chemistry 80)

    SpringerーVerlag  2012 

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  • 高機能デバイス用耐熱性高分子材料の最新技術

    シーエムシー出版  2011 

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  • 使える!有機合成反応241実践ガイド

    化学同人  2010 

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  • 高性能蓄電池-設計基礎研究から開発・評価まで-

    株式会社 エヌ・ティー・エス  2009 

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  • 最新リチウムイオン二次電池〜安全性向上および高機能性に向けた材料開発〜

    株式会社情報機構  2008 

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  • 光学用透明樹脂における材料設計と応用技術

    株式会社技術情報協会  2007 

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    丸善  2000 

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  • クロスカップリング反応を利用した有機薄膜太陽電池用ポリマーの開発 Invited

    森 裕樹, 西原康師

    月刊ファインケミカル   49 ( 11 )   12 - 20   2020.11

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  • 新規アクセプター部位を含むπ共役系高分子の開発と有機薄膜太陽電池への応用 Invited

    森 裕樹, 西原康師

    化学工業   68 ( 11 )   37 - 45   2017

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  • 高原子価遷移金属を利用する有機合成反応―新しい触媒サイクル設計への指針 Invited

    奥田靖浩, 西原康師

    化学   70 ( 10 )   68 - 69   2015

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  • π 共役系分子を用いる有機電界効果トランジスタの最前線 (共著)

    森裕樹, 西原康師

    高分子   63 ( 12 )   866 - 870   2014

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  • Isomerization of (Z)-alkenylsilanes to (E)-isomers with hydrosilane and RhI(PPh3)3

    Mori Atsunori, Takahisa Eisuke, Nishihara Yasushi, Hiyama Tamejiro

    Canadian Journal of Chemistry   79 ( 11 )   1522 - 1524   2001.11

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Presentations

  • Phenanthro[1,2-b:1,7-b’]dithiophene (PDT): Application to organic field-effect transistors and photovoltaics Invited

    Yasushi Nishihara

    ICCHD-20  2020.1.8 

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    Event date: 2020.1.7 - 2020.1.9

    Language:English   Presentation type:Oral presentation (invited, special)  

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  • Development of Organic Solar Cells Based on New Acceptor Units in Semiconducting Polymers Invited

    Yasushi Nishihara

    2019 Annual Meeting of the International Collaborative ‘111’ Project Based on “Reticular Chemistry of Porous Polymers”  2019.11.16 

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    Event date: 2019.11.16 - 2019.11.17

    Language:English   Presentation type:Oral presentation (invited, special)  

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  • Phenanthro[1,2-b:1,7-b’]dithiophene (PDT): Application to Organic Field-Effect Transistors (OFETs) and Organic Photovoltaics (OPVs) Invited

    Yasushi Nishihara

    The 45th Congress on Science and Technology of Thailand (STT45)  2019.10.8 

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    Event date: 2019.10.7 - 2019.10.9

    Language:English   Presentation type:Oral presentation (invited, special)  

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  • Phenanthro[1,2-b:1,7-b’]dithiophene (PDT): Application to Organic Field-Effect Transistors (OFETs) and Organic Photovoltaics (OPVs) Invited

    Yasushi Nishihara

    International Symposium on Catalysis and Fine Chemicals 2018 (C&FC2018)  2018.10.10 

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    Event date: 2018.10.10 - 2018.10.14

    Language:Japanese  

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  • 機能性マテリアル創出のための有機金属錯体触媒 Invited

    西原康師

    第7回 CSJ 化学フェスタ 2017  2017.10.18 

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    Event date: 2017.10.17 - 2017.10.19

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

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  • Nickel or Palladium-Catalyzed Decarbonylative Transformations of Acyl Fluorides Invited

    Yasushi Nishihara

    The International Symposium on Advanced Science and Technology (ISAST)  2020.10.16 

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  • 錯体から有機半導体まで―私が資源研で学んだ多くのこと― Invited

    西原康師

    資源化学研究所創立80年記念学術シンポジウム  2019.11.22 

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    Language:Japanese   Presentation type:Oral presentation (invited, special)  

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  • クロスカップリングを用いる有機半導体材料の創製 Invited

    西原康師

    第2回SPERC 計算化学講演会~有機材料創製ミニシンポジウム~  2019.11.13 

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    Language:Japanese   Presentation type:Oral presentation (invited, special)  

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  • クロスカップリングを利用するフェナセン型分子の合成と電子エネルギーデバイスへの応用

    第29回万有札幌シンポジウム  2017 

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  • Effects of alkyl side-chains and molecular weights on photovoltaic property in phenanthrodithiophene-based semiconducting polymers

    PACCON2017  2017 

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  • 含硫黄フェナセン型分子の開発と有機電子エネルギーデバイス素子への応用

    第43回中国四国地区高分子講座  2017 

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  • Development of High-Performance Organic Photovoltaic Cells Containing the Phenanthrodithiophene (PDT) Unit

    E-MRS (European Materials Research Society) 2016 Fall  2016 

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  • Synthesis of Substituted Picenes through Pd-Catalyzed Cross-Coupling Reaction/Annulation Sequences and Their Physicochemical Properties

    International Symposium on Frontiers of Organometallic Chemistry  2013 

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  • Highly Regio- and Stereoselective Synthesis of Multi-substituted Olefins from Alkynylboronates

    International Symposium of Homogenous Reactivity  2013 

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  • クロスカップリング反応を用いるフェナセン型分子の合成と物性

    分子研シンポジウム  2013 

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  • パラジウム触媒によるノルボルナジエンのシアノエステル化反応の開発と開環メタセシス重合によるポリシクロオレフィンの合成

    高分子学会中国四国支部 高分子研究科  2012 

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  • Highly Selective Synthesis of Multi-substituted Olefins through Carbozirconation of Alkynylboronates and Sequential Cross-Couplings

    2nd International Conference on Molecular & Functional Catalysis (ICMFC-2),  2012 

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  • 遷移金属を用いるカルボメタル化による選択的多置換オレフィンの合成

    近畿化学協会 有機金属部会平成22年度第4回例会  2011 

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  • アルキニルボロン酸エステルのカルボジルコネーションとそれに続く根岸および鈴木-宮浦カップリングによる多置換オレフィン類の位置および立体選択的合成

    有機合成化学協会中国四国支部 ミニシンポジウム2011 in 愛媛  2011 

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  • 開環メタセシス重合とそれに続く水素化によるシアノ基とエステル基を同時に有するポリノルボルネンの合成

    第60回高分子討論会  2011 

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  • Highly Regio- and Stereoselective Synthesis of Multi-alkylated Olefins by Zirconocene-Mediated Transformation of 1-Alkynylboronates and Sequential Negishi and Suzuki-Miyaura Cross-Coupling Reactions

    14th Asian Chemical Congress (14th ACC)  2011 

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  • Synthesis of Doubly Functionalized Norbornenes and Ru-Catalyzed Ring-Opening Metathesis Polymerization

    China-Japan Symposium on Catalytic Organic Synthesis  2010 

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  • 銅触媒によるアルキニルシランとヨウ化アリールの交差カップリング反応

    第57回有機金属化学討論会  2010 

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  • Palladium/Copper-Cocatalyzed Sonogashir-Type Cross-Coupling Reactions of Aryl Halides with Alkynylsilanes via a Direct Carbon-Silicon Bond Cleavage

    The 24th International Conference on Organometallic Chemistry (ICOMC2010)  2010 

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  • Palladium/Copper-Catalyzed Sila-Sonogashira Cross-Coupling Reactions of Aryl Halides with Alkynylsilanes via a Direct C-Si Bond Activation under a Neutral Condition

    11th Tetrahedron Symposium  2010 

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  • パラジウム錯体を触媒として用いるシアノエステル化反応と反応機構の解明

    大阪市立大学談話会  2010 

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  • パラジウム触媒によるノルボルネン類のシアノエステル化反応の開発と新規電子光学ポリマー合成への応用

    有機化学研究会(白鷺セミナー)  2010 

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  • Highly Regio- and Stereoselective Synthesis of Multi-substituted Olefins from Alkynylmetallic Species and Its Application toward Anti-cancer Agents

    第3回 高度医療都市を創出する未来技術国際シンポジウム-抗がん剤・抗感染症創薬のための標的分子探求-  2010 

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  • Highly Efficient and Selective Synthesis of Multisubstituted Olefins from Alkynylboronates Mediated by a Zirconocene Complex

    The International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)  2010 

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  • Zirconocene-Mediated Highly Regio- and Stereoselective Synthesis of Multi-substituted Olefins from Alkynylmetallic Species

    The 6th International Symposium on Integrated Synthesis (ISIS-6)  2010 

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  • Cross-Coupling Reactions of Aryl Halides with Alkynylsilanes Catalyzed by Palladium and Copper

    The 16th Malaysian Chemical Congress (16MCC), Kuala Lumpur  2010 

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  • Synthesis of Doubly Functionalized Norbornenes and Control of the Polymer Molecular Weights by Living Ring-Opening Metathesis Polymerization

    Second Japan-Singapore Bilateral Symposium on Catalysis  2009 

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  • ジルコノセン錯体とアルキニルシランを用いる高選択的多置換アルケニルシランの合成

    日本化学会第89春季年会  2009 

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  • コバルト触媒を用いる根岸型アルキル-アリールクロスカップリング

    日本化学会第89春季年会  2009 

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  • Palladium-Catalyzed Cyanoesterification of Norbornenes and Mechanistic Implications

    Symposium in Commemoration of International Exchange Agreement between Faculty of Science, University of Copenhagen, Denmark and Graduate School of Natural Science and Technlogy, Okayama University  2009 

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  • Palladium-catalyzed sila-Sonogashira Cross-Coupling Reactions of Alkynylsilanes with Aryl Iodides under Neutral Conditions

    The First International Symposium of Chemistry and Biochemistry in East Asia  2009 

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  • Synthesis and Examination of polymerization activity of Nickel(II) Complexes Tethered by Nitrogen-Oxygen Bidentate Ligand

    The First International Symposium of Chemistry and Biochemistry in East Asia  2009 

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  • 遷移金属錯体による結合活性化法の開発と機能性分子合成への応用

    第26回有機合成化学セミナー  2009 

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  • Highly Efficient and Selective Synthesis of Anticancer Agent Tamoxifen Mediated by a Zirconocene Complex

    13th Asian Chemical Congress (13th ACC)  2009 

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  • 二置換型極性ノルボルネンのHPLC による光学分割と開環メタセシス重合によるキラルポリマーの合成

    第56回有機金属化学討論会  2009 

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  • ジルコノセン錯体とアルキニルスズ化合物の反応

    日本化学会第89春季年会  2009 

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  • ジルコニウム錯体を用いる乳癌の治療薬タモキシフェンの効率的合成

    第2回高度医療都市を創出する未来技術国際シンポジウム〜先端テクノロジーの総合戦略 がんと感染症を考える〜  2009 

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  • パラジウム触媒を用いるアルキニルシランとヨウ化アリールの交差カップリング反応

    日本化学会第89春季年会  2009 

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  • Synthesis and Optical Rotation of Chiral Doubly Functionalized Polar Polynorbornenes

    The First International Symposium of Chemistry and Biochemistry in East Asia  2009 

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  • Reactions of Alkynylstannanes with a Zirconocene Complex

    The First International Symposium of Chemistry and Biochemistry in East Asia  2009 

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  • ジルコニウム錯体を用いる乳癌の治療薬タモキシフェンの効率的合成

    第2回高度医療都市を創出する未来技術国際シンポジウム~先端テクノロジーの総合戦略 がんと感染症を考える~  2009 

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  • ジルコノセン錯体を用いる立体選択的アルケニルシラン合成と交差カップリング反応における置換基効果

    日本化学会第89春季年会  2009 

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  • ジルコノセン錯体と有機ホウ素化合物を用いる効率的かつ高選択的多置換オレフィン合成

    第93回有機合成シンポジウム  2008 

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  • Palladium-Catalyzed Thioesterification with Arylthioformates across Norbornadiene

    Taiwan-Japan International Symposium on Organic Chemistru and Molecular Science  2008 

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  • 乳癌の抗癌剤タモキシフェンの効率的全合成

    高度医療都市を創出する未来技術シンポジウム〜先端テクノロジーの総合戦略 がんと感染症を考える〜  2008 

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  • Synthesis and Structural Analysis of Nickel(II) Complexes Tethered by Nitrogen-Oxygen Bidentate Ligands

    Taiwan-Japan International Symposium on Organic Chemistru and Molecular Science  2008 

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  • Palladium-Catalyzed Cyanoesterification of Norbornenes and Its Application to Opto-electronic Polymers

    Taiwan-Japan International Symposium on Organic Chemistru and Molecular Science  2008 

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  • パラジウム触媒を用いるノルボルナジエンのチオエステル化反応

    日本化学会第88春季年会  2008 

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  • ジルコノセン(II) 錯体とアルキニルシランの反応

    日本化学会第88春季年会  2008 

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  • 光学活性2置換型極性ポリノルボルネン類の合成と旋光性

    日本化学会第88春季年会  2008 

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  • 二置換型極性ノルボルネンの合成およびリビング開環メタセシス重合によるポリマーの分子量制御

    日本化学会第88春季年会  2008 

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  • 新規トリポッド配位子を有するロジウム触媒によるアリール亜鉛化合物のアルキル化

    日本化学会第88春季年会  2008 

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  • ロジウム触媒を用いるアリール亜鉛化合物の酸化的カルボニル化によるジアリールケトン合成

    日本化学会第88春季年会  2008 

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  • Synthesis of Unsymmetrical Diarylethynes by the Cross-Coupling Reaction ofAlkynylsilanes with Aryl Chlorides

    The 15th International Symposium on Organosilicon Chemistry  2008 

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  • Efficient Synthesis of an Anti-cancer Agent, (Z)-Tamoxifen from an Alkynylboronate Mediated by a Zirconocene Complex

    Third International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability  2008 

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  • パラジウム触媒によるアルキニルシランと塩化アリールのシラ薗頭カップリング反応

    第55回有機金属化学討論会  2008 

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  • 酸素-窒素型二座配位子を有するニッケル(II)錯体の合成と構造解析

    第55回有機金属化学討論会  2008 

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  • 根岸型アルキル-アリールクロスカップリング:配位性官能基を有するホスフィン配位子によるβ-水素脱離の抑制

    第55回有機金属化学討論会  2008 

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  • Zirconocene-Mediated Highly Efficient and Selective Synthesis of Multisubstituted Olefins from Alkynylboronates and Its Application

    The 13th International Coference on Boron Chemistry (ImeBoron XIII),  2008 

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  • Synthesis and Thermal Properties of Novel Polynorbornenes by Ru-Initiated Ring-Opening Metathesis Polymerization and the Subsequent Ru-Catalyzed Hydrogenation

    The 23rd International Coference on Organometallic Chemistry (ICOMC2008)  2008 

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  • Zirconocene-Mediated Highly Efficient and Selective Synthesis of Multisubstituted Olefins from Alkynylboronates

    The 11th Osaka City University International Conference "New Horizons of Molecular Science Dispatched from Asia"  2007 

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  • Synthesis of Novel Cycloolefin Polymers by Ru-Initiated Ring-Opening Metathesis Polymerization and Subsequent Ru-Catalyzed Hydrogenation of Doubly Functionalized Norbornenes with Both Cyano and Ester Groups

    The 14th Organometallic Chemistry towards Organic Synthesis (OMCOS-14)  2007 

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  • Zirconocene-Mediated Highly Selective and Facile Synthesis of 1,2-Diaryl-1-butenes from Alkynylboronates

    Second International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability International Conference on Asymmetric Organocatalysis  2007 

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  • 含ホウ素有機―無機複合ポリマーのリチウムイオン伝導性と全固体二次電池への応用

    日本化学会第87春季年会  2007 

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  • ジルコノセン錯体を用いる1,2-ジアリールブテンの位置および立体選択的合成

    日本化学会第87春季年会  2007 

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  • ルテニウムヒドリド触媒による二置換型極性ポリノルボルネン類の水素添加

    日本化学会第87春季年会  2007 

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  • 二置換型極性ポリノルボルネン類のエステル基上の置換基効果

    日本化学会第87春季年会  2007 

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  • オレフィンメタセシスにより得られた2官能性アリールボロン酸をモノマーとするポリマー電解質の合成

    日本化学会第87春季年会  2007 

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  • 新規テトラアリールペンタボラート骨格を含むリチウムイオン2次電池のための有機―無機複合ポリマー電解質の合成

    日本化学会第87春季年会  2007 

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  • ロジウム触媒を用いるアリール亜鉛化合物とホスホリル基を持つアルキルヨウ化物とのクロスカップリング反応

    日本化学会第87春季年会  2007 

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  • Zirconocene-Mediated Total Synthesis of (Z)-Tamoxifen Starting from 1-Alkynylboronates

    3rd China-Japan Symposium On Chemistry  2007 

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  • パラジウム触媒を用いるノルボルナジエンへのチオエステル化反応

    2007年日本化学会西日本大会  2007 

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  • ルテニウムヒドリド触媒による二置換型極性ポリノルボルネン類の水素化反応と置換基効果

    2007年日本化学会西日本大会  2007 

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  • 触媒的クロスカップリングによるホスホリル置換アルキルアレーン類の合成

    2007年日本化学会西日本大会  2007 

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  • ロジウム触媒を用いるアリール金属化合物の酸化的カップリング

    2007年日本化学会西日本大会  2007 

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  • ジルコノセン錯体による多置換オレフィン類の位置選択的合成

    2007年日本化学会西日本大会  2007 

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  • パラジウム触媒によるノルボルネン類のシアノエステル化の中間体-アルコキシ(シアノ)パラジウム(II)錯体の合成と構造

    第54回有機金属化学討論会  2007 

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  • ルテニウム触媒による二置換型極性ポリノルボルネン類の水素添加とエステル基上の置換基効果

    第54回有機金属化学討論会  2007 

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  • ジルコノセン錯体とアルケニルホウ素化合物を用いる多置換オレフィン類の効率的かつ高選択的合成

    第54回有機金属化学討論会  2007 

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  • パラジウム触媒によるノルボルネン類のシアノエステル化反応と新規機能性光学材料への応用 (依頼講演)

    第23回若手化学者のためのセミナー(化学道場)  2007 

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  • パラジウム触媒を用いるノルボルナジエンのシアノエステル化反応

    日本化学会第86春季年会  2006 

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  • アリール亜鉛化合物を用いる官能基をもつアリールアレンの合成

    日本化学会第86春季年会  2006 

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  • ロジウム触媒を用いるアリール亜鉛化合物とハロゲン化アリールとのクロスカップリング

    日本化学会第86春季年会  2006 

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  • パラ-フェニレンジ亜鉛化合物の逐次的クロスカップリング反応:配位子効果の検討

    日本化学会第86春季年会  2006 

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  • 極性シクロオレフィンポリマーの開発を目指した置換ノルボルネン類の合成と反応性

    「シクロオレフィンポリマーの特性と応用」講習会  2006 

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  • 新規機能性光学材料を指向したシアノ基とエステル基を同時に有するポリシクロオレフィンの合成

    2006年日本化学会西日本大会 2H06  2006 

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  • Synthesis of Doubly Functionalized Polar Norbornenes by the Palladium-Catalyzed Cyanoesterification

    The 10th International KYOTO Conference on New Aspects of Organic Chemistry (IKCOC-10), PA-016  2006 

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  • アルコキシカルボニル(シアノ)パラジウム (II) 錯体とノルボルナジエンの反応

    第56回錯体化学討論会  2006 

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  • ルテニウムカルベン錯体を開始剤として用いる2官能性極性ノルボルネン誘導体のリビング開環メタセシス重合

    第53回有機金属化学討論会  2006 

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  • ノルボルネン類のシアノエステル化反応とその生成物をモノマーとする開環メタセシス重合反応〜新規光学系材料の実用化を目指して〜

    若手研究者の会  2006 

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  • 二置換型極性ノルボルネン類の合成と重合反応

    第55回高分子学会年次大会  2006 

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  • リチウムイオン電池の大型化を目指した含ホウ素有機-無機複合固体電解質の創製

    「自動車用リチウムイオン二次電池の高出力化,長寿命化と安全性評価」講習会  2006 

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  • 二置換型極性ノルボルネン類の開環メタセシス重合

    日本化学会第86春季年会  2006 

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  • アルコキシカルボニル(シアノ)パラジウム (II) 錯体の合成と反応

    日本化学会第86春季年会  2006 

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  • リチウムイオン電池の電解質を指向した含ホウ素有機―無機複合ポリマーの合成と物性(2)

    第46回電池討論会  2005 

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  • リチウムイオン電池の電解質を指向した含ホウ素有機―無機複合ポリマーの合成と物性(1)

    第46回電池討論会  2005 

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  • パラジウム触媒を用いるノルボルネン類のシアノエステル化反応

    第52回有機金属討論会  2005 

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  • Copper-Mediated Homocoupling Reactions of Alkynylboronates Affording Symmetrical Conjugate Diynes

    12th International Conference on Boron Chemistry (MEBORON-XII)  2005 

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  • A Preparative Synthetic Method of Ketones by Cross-Coupling Reactions of Acid Chlorides with Organoboron Compounds

    The 13rd Organometallic Chemistry towards Organic Synthesis (OMCOS-13)  2005 

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  • 銅塩とパラジウム触媒を用いるアリールボロン酸と酸クロリドの交差カップリング反応

    日本化学会第85春季年会  2005 

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  • フェニレンジ亜鉛化合物への求電子剤の逐次的導入

    日本化学会第85春季年会  2005 

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  • ロジウム触媒を用いるアリール亜鉛化合物のアルキル化

    日本化学会第85春季年会  2005 

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  • 銅塩を用いるアルキニルボロン酸エステルと酸クロリドの交差カップリング反応

    日本化学会第85春季年会  2005 

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  • 銅塩を用いるアルキニルボロン酸エステル類のホモカップリング反応

    日本化学会第85春季年会  2005 

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  • アルキニルボロン酸エステルと銅塩の反応によるアルキニル銅種の生成とその反応性

    日本化学会第85春季年会  2005 

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  • アリール配位子へのフッ素原子の導入による重要中間体の単離と構造解析

    第11回フッ素化学セミナー「含フッ素リガンドの展開」  2004 

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  • ホスフィド架橋をもつ環状三核ヒドリド白金錯体と有機ケイ素化合物の反応

    第84日本化学会春季年会  2004 

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  • アリール(ヒドロキソ)パラジウム(II) 錯体と有機ホウ素化合物の反応

    第84日本化学会春季年会  2004 

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  • メトキソおよびヒドロキソロジウム(I) 錯体とアリールボロン酸エステルの反応

    第84日本化学会春季年会  2004 

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  • ホスフィド架橋をもつ環状三核ヒドリド白金錯体と有機ホウ素化合物との反応

    第84日本化学会春季年会  2004 

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  • 遷移金属錯体と有機ホウ素化合物の反応—トランスメタル化反応を鍵として

    第36回有機金属化学若手の会夏の学校  2003 

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  • Synthesis and Structural Characterization of the First Unsymmetrical Diarylpalladium Complexes trans-Pd(C6F5)(2,4,6-C6F3H2)(PEt3)2 from Arylboronic Acid 2,4,6-C6F3H2B(OH)2 and trans-PdI(C6F5)(PEt3)2

    The 12nd Organometallic Chemistry directed towards Organic Synthesis (OMCOS-12)  2003 

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  • 低原子価白金錯体と二級ホスフィンとの反応によるジホスフィド架橋多核白金(II) 錯体の合成

    第81日本化学会春季年会  2003 

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  • アリール(ヨード)パラジウム(II) および白金(II)錯体とアリールボロン酸の反応におけるホスフィン類の効果

    第81日本化学会春季年会  2003 

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  • アリーロキソまたはメトキソロジウム(I) 錯体とボロン酸エステルとの反応

    第81日本化学会春季年会  2003 

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  • アリールオキソロジウム(I) 錯体とアリールボロン酸との反応による新規ペンタボラートアニオンの合成

    第81日本化学会春季年会  2003 

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  • アリール(トリフラート)パラジウム(II)錯体とアリールボロン酸の反応による非対称ジアリールパラジウム(II)錯体の生成

    第53回錯体化学討論会  2003 

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  • アルコキソロジウム(I) 錯体 [Rh(OR)(cod)]2 (R = Me, Et, tBu) とアリールボロン酸エステルとの反応

    第53回錯体化学討論会  2003 

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  • 架橋有機リン配位子をもつ直線状白金多核錯体の合成

    第53回錯体化学討論会  2003 

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  • アリール(ハロゲノ)白金(II) 錯体と有機ホウ素化合物の反応におけるホスフィン配位子の効果

    第53回錯体化学討論会  2003 

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  • 選択的な3員環の開環を伴う1-メチレン-4-フェニル-スピロ[2.2]ペンタンとロジウム(I) ヒドリド錯体との反応

    第52回錯体化学討論会  2002 

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  • Synthesis of Tetraarylpentaborates from Reaction of Arylboronic Acids with an Aryloxorhodium Complex.

    35th International Conference on Coordination Chemistry  2002 

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  • アリーロキソまたはメトキソロジウム(I) 錯体とボロン酸エステルとの反応

    第81日本化学会春季年会  2002 

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  • 白金触媒を用いるメチレンシクロプパン類の異性化反応

    第81日本化学会春季年会  2002 

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  • ロジウム(I) ヒドリド錯体と1-メチレン-4-フェニル-スピロ[2.2]ペンタンとの反応

    第81日本化学会春季年会  2002 

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  • ロジウム(I)アリーロキソ錯体とアリールボロン酸との反応によるスピロ型ボロキシナートアニオンの合成

    第81日本化学会春季年会  2002 

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  • アリールオキソロジウム(I)錯体とアリールボロン酸との反応による含ホウ素アニオンの合成

    子研研究会,無機金属化学の展望―全元素化学を目指して  2002 

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  • アリール(ハロゲノ)白金(II)錯体とアリールボロン酸の反応におけるトランスメタル化

    第52回錯体化学討論会  2002 

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  • ロジウム(I)アリールオキソ錯体とアリールボロン酸エステルとの反応

    第52回錯体化学討論会  2002 

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  • シリルロジウム(III) およびイリジウム(III) 錯体のケイ素—塩素結合生成反応—中心金属,シリル配位子による反応性の違い

    第47回有機金属化学討論会  2002 

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  • Preparation, Characterization, and Reactivities of Novel Boryloxorhodium Complexes.

    The 224th ACS National Meeting  2002 

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  • Rhodium(III) and Iridium(III) Complexes with Halo and Alkoxysilyl Ligands. Relative Stability of the Metal–Silicon Bond and Elimination of Halosilanes.

    20th International Conference on Organometallic Chemistry  2002 

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  • Highly selective C-C bond activation of methylenecyclopropanes by transition metal complexes

    シンポジウム:有機金属化学の最先端  2002 

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  • Vaska 錯体とヒドロシラン類との反応におけるケイ素上の置換基の違いとクロロシランの還元的脱離速度に関する研究

    第7回ケイ素化学協会シンポジウム  2002 

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  • メチレンシクロプロパンの化学–錯体から有機合成まで–,

    錯体化学若手の会ミニシンポジウム  2002 

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  • 有機パラジウム錯体とアリールホウ素化合物の反応

    第52回錯体化学討論会  2002 

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  • アリーロキソおよびヒドロキソロジウム(I)錯体と有機ホウ素化合物との反応

    第51回錯体化学討論会  2001 

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  • イリジウム(I)ヒドリド錯体と2,2-ジアルキル-1-メチレンシクロプロパンとの反応

    第79日本化学会春季年会  2001 

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  • 2,2-ジアルキル置換メチレンシクロプロパンとロジウムおよびイリジウムヒドリド錯体との反応—ビニル錯体の生成と異性化—

    第51回錯体化学討論会  2001 

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  • Ring-Opening Isomerization of Methylenecyclopropopanes into 1,3-Dienes Promoted by Transition Metal Hydrido Complexes.

    Post-OMCOS  2001 

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  • 白金触媒によるメチレンシクロプロパン類のヒドロシリル化反応における中間錯体の単離と同定

    第51回錯体化学討論会  2001 

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  • ロジウム(I)ヒドロキソ錯体と有機ボロン酸との反応

    第79日本化学会春季年会  2001 

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  • 遷移金属錯体触媒を用いるメチレンシクロプロパン類のヒドロシリル化反応

    第79日本化学会春季年会  2001 

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  • 白金(II)カチオン錯体へのシラノール上の有機基のトランスメタル化反応—ケイ素–炭素結合の活性化における機構の考察—

    第79日本化学会春季年会  2001 

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  • ロジウム(I)ヒドリド錯体と2,2-ジアルキル-1-メチレンシクロプロパンとの反応

    第79日本化学会春季年会  2001 

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  • ハロゲノ(ヒドリド)シリルロジウム(III) 錯体の安定性と反応性に及ぼすハロゲンの影響

    第6回ケイ素化学協会シンポジウム  2001 

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  • 白金錯体を触媒とするメチレンシクロプロパン類のヒドロシリル化反応

    第47回有機金属化学討論会  2001 

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  • リン配位子をもたないロジウム(I) 錯体と有機ボロン酸との反応

    第51回錯体化学討論会  2001 

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  • 銅(I) 塩を用いるアルキニルシランのカップリング反応を利用するビスフェノールA誘導体ユニットを含む高分子の合成

    第78日本化学会春季年会  2000 

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  • 白金(II)錯体によるシラノールのケイ素–炭素結合の活性化と有機基のトランスメタル化反応

    第50回錯体化学討論会  2000 

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  • Isolation of Intermediates of Ring-opening Isomerization of Methylenecyclopropanes Promoted by Rh(I) and Ir(I) Complexes..

    34th International Conference on Coordination Chemistry  2000 

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  • シランジオールの合成とパラジウム触媒を用いるカップリング反応

    第78日本化学会春季年会  2000 

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  • 3,3,3-トリフルオロプロピル基を有するシラノールの交差カップリングと Mizoroki-Heck 型反応

    第78日本化学会春季年会  2000 

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  • New C-C and C-H Bond Activation of 1-Methylenecyclopropanes Promoted by Hydrido Complexes of Rh(I) and Ir(I).

    2000 International Chemical Congress of Pacific Basin Societies (Pacifichem ‘2000)  2000 

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  • フッ化テトラブチルアンモニウムを活性化剤に用いる末端アルキンの交差カップリング反応

    第46回有機金属討論会  2000 

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  • 同一分子内にアルキニルシランとトリフラートを有する化合物の交差カップリングを用いる重合反応

    第78日本化学会春季年会  2000 

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  • メチレンシクロプロパンの炭素–炭素結合の活性化を伴うロジウム(I)錯体上での配位子骨格変換反応

    第50回錯体化学討論会  2000 

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  • ロジウム (I)ヒドリド錯体とメチレンシクロプロパンの反応とその機構的考察

    第78日本化学会春季年会  2000 

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  • アルキニル基のケイ素から銅へのトランスメタル化の機構的考察

    第78日本化学会春季年会  2000 

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  • ロジウム(I)およびイリジウム(I)ヒドリド錯体を用いる1-メチレンシクロプロパン類の新規な炭素–炭素,炭素-水素結合の活性化

    第47回有機金属討論会  2000 

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  • ロジウム(I)アリーロキシ錯体の有機金属化合物との反応

    第50回錯体化学討論会  2000 

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  • 新しいシリルロジウム錯体の合成とアセチレンとの反応

    第50回錯体化学討論会  2000 

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  • アルキニルシランとアリールトリフラートの交差カップリング反応を利用する高分子合成

    第76日本化学会春季年会  1999 

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  • 立体選択的ヒドロシリル化を利用する含ケイ素高分子の合成

    第76日本化学会春季年会  1999 

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  • パラジウム触媒を用いるシラノールの交差カップリング反応

    第76日本化学会春季年会  1999 

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  • シラノールおよび有機スズ化合物を用いたMizoroki-Heck 型反応

    第76日本化学会春季年会  1999 

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  • ケイ素上にキラリティーを持つシラノールの合成と光学分割

    第76日本化学会春季年会  1999 

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  • フッ素の配位を利用したSc(OTf)3による脱アセチル化反応

    第76日本化学会春季年会  1999 

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  • アルキニルシランのホモカップリング反応を利用する高分子合成

    第76日本化学会春季年会  1999 

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  • オレフィン・ホスフィン2座配位子をもつジルコノセン錯体の合成と構造

    第49錯体化学討論会  1999 

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  • 銅(I) 塩によるアルキニルシランのカップリング反応を利用する高分子合成

    第77日本化学会秋季年会  1999 

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  • シラノール,シランジオールを用いる炭素—炭素結合形成反応

    第46回有機金属討論会  1999 

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  • 銅(I) 塩を用いる有機ケイ素化合物のカップリング反応とトランスメタル化における機構的考察

    第46回有機金属討論  1999 

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  • Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions of Silanols

    The 216th ACS Meeting  1999 

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  • Homo- and Cross-Coupling Reactions of Alkynylsilanes Mediated by a Copper(I) Salt

    The 216th ACS Meeting  1999 

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Industrial property rights

  • 3,10-ジヒドロキシピセン、3,10-ジヒドロキシピセンの製造方法、屈折率向上剤、並びに、ポリエステル樹脂

    西原康師, 小松伸一, 伊田領二

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    Application no:特願2021-019797  Date applied:2021.2.10

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  • アントラビスチアジアゾール誘導体及びこれを用いて得られるπ共役系重合体

    西原康師, 西永周平, 高橋竜輔, 森 裕樹

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    Application no:特願2016-044905  Date applied:2016.3.8

    Announcement no:特開2017-160150  Date announced:2017.9.14

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  • ピセン誘導体、光電変換材料及び光電変換素子

    西原康師, 兵頭恵太, 森 裕樹

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    Application no:特願2016-555186  Date applied:2015.10.14

    Announcement no:特開2014-240483  Date announced:2014.12.25

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  • ピセノジチオフェン化合物、有機半導体材料、有機半導体層、有機半導体

    西原康師

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    Application no:特願2015-033715  Date applied:2015.2.24

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  • ピセン及びその誘導体の製造方法

    西原康師, 常 寧輝, 岩﨑真之

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    Application no:特願2013-101582  Date applied:2013.5.13

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  • トリアリールエチルエテン誘導体の製造方法

    西原康師

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    Application no:特願2006-252247  Date applied:2006.9.19

    特開2008-74711

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  • エンド位に2個の極性基を有するノルボルネン誘導体,そのメタセシス開環重合体およびそれらの製造方法

    西原康師, 井上善彰

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    Application no:特願2006-64308  Date applied:2006.3.9

    特願2006-064308

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  • ノルボルネン誘導体の開環重合体およびその製造方法

    西原康師, 井上善彰, 高木謙太郎, 田靡正雄, 羽村 敏

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    Application no:特願2005-267127  Date applied:2005.9.14

    特願2005-267127

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  • 2-フルオロ-1-オール類の製造方法

    上代 洋, 森 敦紀, 西原康師, 檜山爲次郎

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    Application no:特願平11-145420  Date applied:1999.5.25

    特開2000-327605

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Awards

  • 2019年度 有機合成化学協会 企業冠賞 富士フィルム・機能性材料化学賞

    2020.2   クロスカップリングを用いるπ共役系有機分子の効率的合成と電子デバイスへの応用

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  • Asian Core Program (ACP) Lectureship Award (Taiwan)

    2018.11   Phenanthro[1,2-b:8,7-b’]dithiophene (PDT): Application to Organic Photovoltaics

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  • 日本学術振興会 科研費審査委員表彰

    2017.8  

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    Country:Japan

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  • 平成29年度 岡山工学振興会 内山勇三科学技術賞

    2017.7   高性能な有機半導体を指向したπ共役分子の設計、合成、機能解明

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    Country:Japan

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  • 平成24年度 岡山工学振興会 科学技術賞

    2012.7   有機薄膜太陽電池用素子ピセン誘導体の高効率合成

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  • 平成21年度 岡山県文化奨励賞(第52回)

    2010.2  

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  • 2008年度有機合成化学奨励賞

    2009.2   遷移金属錯体による結合活性化法の開発と機能性分子合成への応用

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    Country:Japan

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  • 第88春季年会 優秀講演賞(産業)

    2008.5   二置換型極性ノルボルネンの合成およびリビング開環メタセシス重合によるポリマーの分子量制御

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  • 平成19年度岡山大学若手トップリサーチャー

    2007.12  

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    Country:Japan

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  • 第1回岡山大学理学部教育貢献賞

    2007.3  

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    Country:Japan

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  • 第15回有機合成化学協会研究企画賞(日本触媒)

    2003.2   含ホウ素有機無機複合ポリマーの合成とイオン導電性の発現に関する研究

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Research Projects

  • 多官能基を有する多環芳香族化合物の合成と物性評価

    2020.04 - 2022.03

    JXTG エネルギー株式会社  共同研究

    西原康師

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  • 新規π共役系有機分子の効率的な合成および有機電界効果トランジスタへの応用

    2020.04 - 2021.03

    岡山県特別電源所在県科学技術振興事業 

    西原康師

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  • 新規ヘテロアセン化合物類を用いた電子材料への応用研究

    2019.04 - 2021.03

    東ソー有機化学株式会社  共同研究

    西原康師

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  • ジルコノセン錯体を用いる高選択的四置換オレフィンの合成

    2019.04 - 2020.03

    第一稀元素化学工業  2019年度 第一稀元素化学工業助成金 

    西原康師

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  • 原油中に含まれるチオフェン環を有する硫黄化合物の有効利用検討

    2019.04 - 2020.03

    JXTG エネルギー株式会社 

    西原康師

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  • 次世代の再生可能エネルギーとして期待される高効率有機薄膜太陽電池の開発

    2018.04 - 2020.03

    公益財団法人JKA  補助事業部機械振興事業 

    西原康師

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  • 有機合成中間体化合物の新規合成法の開発

    2010.04 - 2022.03

    錦海化学株式会社  共同研究

    西原康師

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  • 有機合成中間体化合物の新規合成法の開発

    2010.04 - 2022.03

    日亜化学株式会社  共同研究

    西原康師

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Class subject in charge

  • Topics in Reaction Chemistry 2 (2021academic year) Concentration  - その他

  • Advanced Reaction Chemistry (2021academic year) Prophase  - 月

  • Synthetic Organic Chemistry (2021academic year) Prophase  - その他

  • Basic Organic Chemistry (2021academic year) 1st and 2nd semester  - 金1,金2

  • Basic Organic Chemistry (2021academic year) 3rd and 4th semester  - 金1,金2

  • Basic Organic Chemistry 1 (2021academic year) 1st semester  - 金1,金2

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  • Basic Organic Chemistry 1 (2020academic year) 1st semester  - 金1,金2

  • Basic Organic Chemistry 1 (2020academic year) Third semester  - 金1,金2

  • Basic Organic Chemistry 1 (2020academic year) Third semester  - 金1,金2

  • Basic Organic Chemistry 1 (2020academic year) 1st semester  - 金1,金2

  • Organic Chemistry 10 (2020academic year) Second semester  - 火1,火2

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  • Organometallic Catalysis (2020academic year) Prophase  - 火3,火4

  • Seminar in Functional Organic Chemistry (2020academic year) Prophase

  • Seminar in Functional Organic Chemistry (2020academic year) Year-round  - その他

  • Seminar in Functional Organic Chemistry (2020academic year) Prophase

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Media Coverage

  • 根岸英一先生を偲んで Newspaper, magazine

    山陽新聞  2021.6

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    Author:Myself 

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