研究者詳細 - 西原　康師

論文 - 西原　康師

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Vinylene‐Bridged Alkoxyfluorobenzothiadiazole (<scp>FOBTzE</scp>)‐Based Semiconducting Polymers for Enhanced Performance in Non‐Fullerene Organic Photovoltaic Cells

Yi Yan, Hiroki Mori, Ryuchi Hosogi, Hiroki Yamane, Tomoki Yoshino, Yasushi Nishihara

Journal of Polymer Science 2024年11月

掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

ABSTRACT

To mitigate the strong aggregation and limited solubility observed in the previously reported vinylene‐bridged alkoxyfluorobenzothiadiazole (FOBTzE)‐based polymer, PFOE4T, we designed and synthesized PBFOE‐1. This novel semiconducting polymer, based on the FOBTzE framework, incorporates an alkylthienyl‐substituted benzodithiophene (BDT) as the donor unit. PBFOE‐1 demonstrated broad and intense absorption between 300 and 700 nm with a relatively wide bandgap of 1.7 eV. Additionally, PBFOE‐1 features a low HOMO energy level (−5.43 eV) compared to PFOE4T (−5.23 eV), likely due to the incorporation of weakly electron‐donating BDT into the polymer backbone. While the PFOE4T/Y12‐based solar cell yielded a modest power conversion efficiency (PCE) of 4.37%, characterized by a short‐circuit current density (J_sc) of 13.5 mA cm⁻², an open‐circuit voltage (V_oc) of 0.69 V, and a fill factor (FF) of 0.47, the PBFOE‐1/Y12 cell exhibited a substantially higher PCE of 10.96%. This improvement is reflected in the enhanced J_sc (23.23 mA cm⁻²), V_oc (0.84 V), and FF (0.56). The superior performance of PBFOE‐1 is primarily attributed to its improved solubility and aggregation behavior, promoting a more ordered face‐on orientation and optimal blend morphology.

DOI： 10.1002/pol.20241036

その他リンク： https://onlinelibrary.wiley.com/doi/pdf/10.1002/pol.20241036

A Highly Efficient Cross‐Coupling Mode via the Release of Small Molecules: Transition Metal‐Catalyzed Unimolecular Fragment Coupling (UFC) 招待査読

Tian Tian, Shuhei Uei, Zhiping Li, Yasushi Nishihara

ChemCatChem 2024年9月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Wiley

Abstract

As a recently developed redox‐neutral coupling reaction, transition‐metal‐catalyzed unimolecular fragment coupling (UFC) has been extensively investigated over the past decade. In comparison to conventional cross‐coupling reactions, cross‐electrophilic coupling (XEC) and cross‐dehydrogenative coupling (CDC) protocols eliminate the need for stoichiometric organometallic reagents, reductants, or oxidants. Additionally, it produces only minimal molecular by‐products for the formation of a series of C−C bonds and C−X bonds with high atom efficiency. This review presents a summary and classification of the research progress made over the past decade in this field. The research is classified into four main categories, decarbonylation, decarboxylation, desulfonylation, and deisocyanation, according to the type of small molecule that is liberated from the reaction system. This facilitates the implementation of more practical, straightforward, and expedient reaction operations. It is noteworthy that the reaction employs carbonyl compounds (aldehydes, ketones, carboxylic acid derivatives, etc.), sulfones, and amides, which are typically inexpensive and accessible, as reaction substrates. This groundbreaking synthetic approach has since yielded a plethora of outcomes and novel research avenues in related fields, while also offering benefits to other related fields.

DOI： 10.1002/cctc.202401190

Thiophene-fused fulminenes (FuDTs): promising platforms for high-mobility organic semiconductors with a zigzag shape 査読

Shohei Kumagai, Takumi Ishida, Shin Kakiuchi, Masakazu Yamagishi, Hiroyasu Sato, Hiroyuki Ishii, Yasushi Nishihara, Toshihiro Okamoto

Chemical Communications 60 ( 79 ) 11152 - 11155 2024年9月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Royal Society of Chemistry (RSC)

[8]Thienophenacene analogues offer excellent single-crystal platforms for hole transport owing to their characteristic molecular orbitals and sufficiently small effective masses.

DOI： 10.1039/d4cc02767a

Palladium-Catalyzed Decarbonylative Nucleophilic Halogenation of Acyl Fluorides and Chlorides: Synthesis of Aryl Halides via Reductive Elimination of the C–X (X = I, Br, and Cl) Bond and Mechanistic Implications 査読

Tian Tian, Myuto Kashihara, Weidan Yan, Yasushi Nishihara

ACS Catalysis 14 ( 16 ) 11905 - 11917 2024年7月

Alkoxy-Substituted Anthrabisthiadiazole–Benzodithiophene-Based Wide-Band-Gap Semiconducting Polymers for High-Performance Non-Fullerene Solar Cells 査読

Hiroki Mori, Ryuchi Hosogi, Yukiya Minagawa, Hiroki Yamane, Yasushi Nishihara

ACS Applied Polymer Materials 6 ( 7 ) 3883 - 3893 2024年3月

Synthesis, Characterization, and Solar Cell Applications of a Non-fused-ring Electron Acceptor Based on Vinylene-bridged Difluorobenzothiadiazole 査読

Hiroki Mori, Natsuki Hasegawa, Tomoki Yoshino, Yasushi Nishihara

Chemistry Letters 52 ( 10 ) 779 - 782 2023年10月

Carboazidation of Terminal Alkenes with Trimethylsilyl Azide and Cyclic Ethers Catalyzed by Copper Powder under Oxidative Conditions 査読

Yuichi Ikemoto, Sho Chiba, Zhenyao Li, Qiang Chen, Hiroki Mori, Yasushi Nishihara

The Journal of Organic Chemistry 88 ( 7 ) 4472 - 4480 2023年3月

Synthesis and solar cell applications of semiconducting polymers based on vinylene-bridged 5-alkoxy-6-fluorobenzo[c][1,2,5] thiadiazole (FOBTzE) 査読

Hiroki Mori, Yuya Asanuma, Ryuchi Hosogi, Yasushi Nishihara

Polymer Journal 55 ( 4 ) 405 - 415 2023年1月

Nickel-Catalyzed Decarbonylative Reductive Alkylation of Aroyl Fluorides with Alkyl Bromides 査読

Qiang Chen, Jingwen You, Tian Tian, Zhenyao Li, Myuto Kashihara, Hiroki Mori, Yasushi Nishihara

Organic Letters 24 ( 50 ) 9259 - 9263 2022年12月

π-Extended Zigzag-Shaped Diphenanthrene-Based p-Type Semiconductors Exhibiting Small Effective Masses 査読

Masato Mitani, Shohei Kumagai, Craig P. Yu, Ayako Oi, Masakazu Yamagishi, Shuhei Nishinaga, Hiroki Mori, Yasushi Nishihara, Daisuke Hashizume, Tadanori Kurosawa, Hiroyuki Ishii, Nobuhiko Kobayashi, Jun Takeya, Toshihiro Okamoto

Advanced Electronic Materials 8 ( 11 ) 2200452 - 2200452 2022年7月

Recent Advances in C-F Bond Activation of Acyl Fluorides Directed toward Catalytic Transformation by Transition Metals, N-Heterocyclic Carbenes, or Phosphines 招待査読

Tian Tian, Qiang Chen, Zhiping Li, Yasushi Nishihara

Synthesis 54 ( 17 ) 3667 - 3697 2022年5月

Effects of Acyloxy Groups in Anthrabisthiadiazole-Based Semiconducting Polymers on Electronic Properties, Thin-Film Structure, and Solar Cell Performance 査読

Hiroki Mori, Yuki Yamada, Yukiya Minagawa, Natsuki Hasegawa, Yasushi Nishihara

Bulletin of Chemical Society of Japan 95 ( 6 ) 942 - 952 2022年4月

Palladium/Copper-Cocatalyzed Arylsilylation of Internal Alkynes with Acyl Fluorides and Silylboranes: Synthesis of Tetrasubstituted Alkenylsilanes by Three-Component 査読

Qiang Chen, Zhenyao Li, Yasushi Nishihara

Organic Letters 24 ( 1 ) 385 - 389 2022年1月

Transmetalation of boronic acids and their derivatives: mechanistic elucidation and relevance to catalysis 招待査読

Kohtaro Osakada, Yasushi Nishihara

Dalton Transactions 51 ( 3 ) 777 - 794 2021年12月

Ni-Catalyzed Decarbonylative Alkynylation of Acyl Fluorides with Terminal Alkynes under Copper-Free Conditions 招待査読

Qiang Chen, Liyan Fu, Jingwen You, Yasushi Nishihara

Synlett 32 ( 15 ) 1560 - 1564 2021年10月

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

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

Chemical Communications 57 ( 73 ) 9276 - 9279 2021年8月

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

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年7月

Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C-F Bond Activation 招待査読

Jingwen You, Qiang Chen, Yasushi Nishihara

Synthesis 53 ( 17 ) 3045 - 3050 2021年4月

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

Liyan Fu, Qiang Chen, Yasushi Nishihara

Chemical Records 21 ( 12 ) 3394 - 3410 2021年4月

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

Liyan Fu, Jingwen You, Yasushi Nishihara

Chemical Communications 57 ( 30 ) 3696 - 3699 2021年3月

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

Yasushi Nishihara, Yasuhiro Nishide, Kohtaro Osakada

Dalton Transactions 50 ( 10 ) 3610 - 3615 2021年2月

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

Masayuki Iwasaki, Yuichi Ikemoto, Yasushi Nishihara

Organic Letters 22 ( 19 ) 7577 - 7580 2020年10月

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

Masayuki Iwasaki, Yasuki Kazao, Takumi Ishida, Yasushi Nishihara

Organic Letters 22 ( 18 ) 7343 - 7347 2020年9月

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招待査読

西原康師

有機合成化学協会誌 78 ( 9 ) 867 - 874 2020年9月

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

Zhenfei Ji, Zeliang Cheng, Hiroki Mori, Yasushi Nishihara

Molecules 25 ( 17 ) 3842 - 3842 2020年8月

Decarboxylative Cross-Coupling of Acyl Fluorides with Potassium Perfluorobenzoates 査読

Liyan Fu, Qiang Chen, Yasushi Nishihara

Organic Letters 22 ( 16 ) 6388 - 6393 2020年8月

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 査読

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

Organic & Biomolecular Chemistry 18 ( 34 ) 6634 - 6642 2020年7月

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

Qiang Chen, Liyan Fu, Yasushi Nishihara

Chemical Communications 56 ( 57 ) 7977 - 7980 2020年6月

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

Xiu Wang, Zhenhua Wang, Takumi Ishida, Yasushi Nishihara

Journal of Organic Chemistry 85 ( 11 ) 7526 - 7533 2020年4月

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 招待査読

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

International Journal of Molecular Sciences 21 ( 7 ) 2447 - 2447 2020年4月

Palladium-Catalyzed Decarbonylative Alkylation of Acyl Fluorides 査読

Liyan Fu, Qiang Chen, Zhenhua Wang, Yasushi Nishihara

Organic Letters 22 ( 6 ) 2350 - 2353 2020年3月

Nickel or Palladium-Catalyzed Decarbonylative Transformations of Carboxylic Acid Derivatives 査読

Zhenhua Wang, Xiu Wang, Yasushi Nishihara

Chemistry An Asian Journal 15 ( 8 ) 1234 - 1247 2020年3月

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

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年12月

Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides 査読

Zhenhua Wang, Xiu Wang, Yasuyuki Ura, Yasushi Nishihara

Organic Letters 21 ( 17 ) 6779 - 6784 2019年9月

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

Yuya Asanuma, Hiroki Mori, Yasushi Nishihara

Chemistry Letters 48 ( 9 ) 1029 - 1031 2019年9月

Nickel/copper-cocatalyzed decarbonylative silylation of acyl fluorides 査読

Wang Xiu, Wang Zhenhua, Nishihara Yasushi

Chemical Communications 55 ( 71 ) 10507 - 10510 2019年8月

PPh3-Assisted Esterification of Acyl Fluorides with Ethers via C(sp3)–O Bond Cleavage Accelerated by TBAT 招待査読

Zhenhua Wang, Xiu Wang, Yasushi Nishihara

Catalysts 9 ( 7 ) 574 - 574 2019年6月

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 査読

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

Bulletin of the Chemical Society of Japan 92 ( 6 ) 1107 - 1116 2019年5月

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

Xiu Wang, Zhenhua Wang, Yuya Asanuma, Yasushi Nishihara

Organic Letters 21 ( 10 ) 3640 - 3643 2019年5月

Nickel-Catalyzed Decarbonylative Stannylation of Acyl Fluorides under Ligand-Free Conditions 招待査読

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

Molecules 24 ( 9 ) 1671 - 1671 2019年4月

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

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

Chemistry Letters 48 ( 3 ) 281 - 284 2019年3月

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 査読

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

The Journal of Organic Chemistry 84 ( 2 ) 698 - 709 2019年1月

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

Yuya Asanuma, Hiroki Mori, Ryosuke Takahashi, Yasushi Nishihara

Journal of Materials Chemistry C 7 ( 4 ) 905 - 916 2019年1月

Nickel-catalysed decarbonylative borylation of aroyl fluorides 査読

Zhenhua Wang, a, Xiu Wanga, Yasushi Nishihara

Chemical Communications 54 ( 99 ) 13969 - 13972 2018年11月

Development of a Phenanthrodithiophene-Difluorobenzoxadiazole Copolymer Exhibiting High Open-Circuit Voltage in Organic Solar Cells 査読

Hiroki Mori, Ryosuke Takahashi, Yasushi Nishihara

J. Poly. Sci. Part A: Pol. Chem. 56 ( 23 ) 2646 - 2655 2018年10月

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

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

ACS Omega 3 ( 10 ) 13129 - 13140 2018年10月

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

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

Chem. Lett. 47 ( 11 ) 1409 - 1411 2018年9月

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 査読

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

Asian Journal of Organic Chemistry 7 ( 8 ) 1635 - 1641 2018年8月

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 査読

Hiroki Mori, Shuhei Nishinaga, Ryosuke Takahashi, Yasushi Nishihara

Macromolecules 51 5473 - 5484 2018年6月

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

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

Org. Lett. 20 3848 - 3852 2018年6月

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

Hiroki Mori, Yasushi Nishihara

Polymer Journal 50 1 - 11 2018年5月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Nature Publishing Group

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

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 査読

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

Asian J. Org. Chem. 7 1635 - 1641 2018年5月

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

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年5月

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

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

Macromolecules 51 ( 4 ) 1357 - 1369 2018年2月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society

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%.

DOI： 10.1021/acs.macromol.7b02734

Synthesis of a 1,2-Dithienylethene-Containing Donor-Acceptor Polymer via Palladium-Catalyzed Direct Arylation Polymerization (DArP) 招待査読

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

Molecules 23 ( 4 ) 981 - 990 2018年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：MDPI AG

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.

DOI： 10.3390/molecules23040981

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

Shuhei Nishinaga, Hiroki Mori, Yasushi Nishihara

The Journal of Organic Chemistry 83 5506 - 5515 2018年

Direct Thiolation and Selenation of Aryl C─H Bonds Catalyzed by Palladium or Nickel 査読

Masayuki Iwasaki, Yasushi Nishihara

J. Syn. Org. Chem. Jpn. (Yuki Gosei Kagaku Kyokaishi) 76 ( 1 ) 11 - 20 2018年

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

Masayuki Iwasaki, Yasuhiro Araki, Yasushi Nishihara

J. Org. Chem. 82 ( 12 ) 6242 - 6258 2017年6月

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

Hiroki Mori, Shuto Hara, Shuhei Nishinaga, Yasushi Nishihara

MACROMOLECULES 50 ( 12 ) 4639 - 4648 2017年6月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/acs.macromol.7b00778

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

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

ORGANIC LETTERS 19 ( 5 ) 1092 - 1095 2017年3月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/acs.orglett.7b00116

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

Keita Hyodo, Ryota Toyama, Hiroki Mori, Yasushi Nishihara

ACS Omega 2 ( 1 ) 308 - 315 2017年1月

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：American Chemical Society

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

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 査読

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

RSC ADVANCES 7 ( 10 ) 6089 - 6092 2017年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ROYAL SOC CHEMISTRY

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.

DOI： 10.1039/c6ra27455b

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年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：NATURE PUBLISHING GROUP

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.

DOI： 10.1038/srep38535

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年8月

記述言語：日本語出版者・発行元：SOC SYNTHETIC ORGANIC CHEM JPN

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.

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年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：WILEY-V C H VERLAG GMBH

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.

DOI： 10.1002/tcr.201600017

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年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/acs.orglett.6b00503

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年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ROYAL SOC CHEMISTRY

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).

DOI： 10.1039/c5py01878a

Molecular mechanism of palladium-catalyzed cyanoesterification of methyl cyanoformate onto norbornene 査読

石塚拓也, 奥田靖浩, Szilagyi, R. K, 森聖治, 西原康師

Dalton Trans. 45 ( 18 ) 7786 - 7793 2016年

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

Masayuki Iwasaki, Yasushi Nishihara

DALTON TRANSACTIONS 45 ( 39 ) 15278 - 15284 2016年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ROYAL SOC CHEMISTRY

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.

DOI： 10.1039/c6dt02167k

Synthesis of Multisubstituted Triphenylenes and Phenanthrenes by Cascade Reaction of o-Iodobiphenyls or (Z)-β-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

J. Org. Chem. 80 ( 18 ) 9247 - 9263 2015年9月

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年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

DOI： 10.1246/cl.150357

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年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/acs.macromol.5b00622

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) 査読

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

Journal of Materials Chemistry C 3 ( 12 ) 2960 2015年3月

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：WILEY-BLACKWELL

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

DOI： 10.1002/pola.27500

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年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ROYAL SOC CHEMISTRY

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, <mu >, 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 <|V-th|> of similar to 11 V, was implemented, together with the above high <mu > 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.

DOI： 10.1039/c4tc02413c

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年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHINESE CHEMICAL SOC

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.

DOI： 10.1039/c5qo00039d

Recent progresses in organic field effect transistors based on π-conjugated organic molecules

Hiroki Mori, Yasushi Nishihara

Kobunshi 63 ( 12 ) 866 - 870 2014年12月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Society of Polymer Science

Organic field-effect transistors (OFETs) have gained considerable interest as the key elements for realizing future ubiquitous electronics because they have a large number of advantages such as the flexibility, light-weight, and ease of design. In this article, recent material developments in this field, including phenacene-type molecules, thienoacene derivatives, and a series of donor-acceptor (D-A)-type polymers, are summarized. Phenacene-type molecules possess a low HOMO level and a wide band gap. Recently, among phenacene-type molecules, picene, [6]phenacene, and [7]phenacene have been recognized as unique molecules because using them high field-effect mobility in the transistors can be realized. In addition, in some cases the FET properties were found to be highly improved by an incorporation of alkyl chains to the parent motif and one can expect to apply these molecules to a solution-process owing to a high solubility in common organic solvents. Furthermore, recent progress of diketopyrrolopyrrole (DPP) and isoindigo (IID)-based D-A polymers showing high mobility are introduced.

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年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/jo502274t

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

Masayuki Iwasaki, Tomoya Fujii, Kiyohiko Nakajima, Yasushi Nishihara

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 53 ( 50 ) 13880 - 13884 2014年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：WILEY-V C H VERLAG GMBH

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.

DOI： 10.1002/anie.201408121

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

Masayuki Iwasaki, Yuta Tsuchiya, Kiyohiko Nakajima, Yasushi Nishihara

ORGANIC LETTERS 16 ( 18 ) 4920 - 4923 2014年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol502439m

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年8月

記述言語：英語出版者・発行元：WILEY-V C H VERLAG GMBH

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.

DOI： 10.1002/ejic.201402168

New Entry to the Synthesis of α-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年7月

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 査読

Keita Hyodo, Hikaru Nonobe, Shuhei Nishinaga, Yasushi Nishihara

TETRAHEDRON LETTERS 55 ( 29 ) 4002 - 4005 2014年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/j.tetlet.2014.05.035

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年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/jo500543h

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

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

CHEMISTRY-A EUROPEAN JOURNAL 20 ( 9 ) 2459 - 2462 2014年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：WILEY-V C H VERLAG GMBH

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.

DOI： 10.1002/chem.201304717

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

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

CHEMISTRY-AN ASIAN JOURNAL 9 ( 1 ) 58 - 62 2014年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：WILEY-V C H VERLAG GMBH

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.

DOI： 10.1002/asia.201301295

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

Keita Hyodo, Masato Suetsugu, Yasushi Nishihara

ORGANIC LETTERS 16 ( 2 ) 440 - 443 2014年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol403326z

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

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

JOURNAL OF ORGANIC CHEMISTRY 79 ( 1 ) 285 - 295 2014年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/jo4024057

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

奥田靖浩, Szilagyi, R. K, 森聖治, 西原康師

Dalton Trans. 43 ( 25 ) 9537 - 9548 2014年

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

李靖, 奥田靖浩, 趙家冀, 森聖治, 西原康師

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

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

西原康師, 木下恵, 兵頭恵太, 奥田靖浩, 江口律子, 後藤秀徳, 浜尾志乃, 高林康裕, 久保園芳博

RSC Advances 3 ( 42 ) 19341 - 19347 2014年

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 査読

奥田靖浩, 岡本尊, 山本有沙, 李靖, 中島清彦, 西原康師

Chem. Lett. 43 ( 4 ) 417 - 419 2014年

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

奥田靖浩, 石黒雄也, 森聖治, 中島清彦, 西原康師

Organometallics 33 ( 7 ) 1878 - 1889 2014年

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

Masayuki Iwasaki, Shohel Lino, Yasushi Nishihara

ORGANIC LETTERS 15 ( 20 ) 5326 - 5329 2013年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/oI4025869

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

Jiao Jiao, Kiyohiko Nakajima, Yasushi Nishihara

ORGANIC LETTERS 15 ( 13 ) 3294 - 3297 2013年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol401333j

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

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

Organic Letters 15 ( 10 ) 2418 - 2421 2013年5月

記述言語：英語掲載種別：研究論文（学術雑誌）

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.

DOI： 10.1021/ol400896u

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 査読

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

TETRAHEDRON 69 ( 12 ) 2565 - 2571 2013年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/j.tet.2013.01.058

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

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

TETRAHEDRON LETTERS 54 ( 6 ) 518 - 521 2013年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/j.tetlet.2012.11.069

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

常寧輝, 森裕樹, 陳璽朝, 奥田靖浩, 岡本尊, 西原康師

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

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

常寧輝, 陳璽朝, 野々部瑛, 奥田靖浩, 森裕樹, 中島清彦, 西原康師

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

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

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

HETEROCYCLES 86 ( 2 ) 933 - 940 2012年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.3987/COM-12-S(N)77

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

Yasushi Nishihara, Daisuke Ogawa, Shintaro Noyori, Masayuki Iwasaki

CHEMISTRY LETTERS 41 ( 11 ) 1503 - 1505 2012年11月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

DOI： 10.1246/cl.2012.1503

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 査読

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

TETRAHEDRON 68 ( 24 ) 4869 - 4881 2012年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/j.tet.2012.03.093

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

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

ORGANIC LETTERS 13 ( 23 ) 6272 - 6275 2011年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol202749x

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年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

DOI： 10.1246/cl.2011.972

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/jo1025173

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年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE BV

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.

DOI： 10.1016/j.apcatb.2011.01.002

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年

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年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol100210u

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年1月

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年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/j.tetlet.2009.11.001

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年9月

記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：SOC SYNTHETIC ORGANIC CHEM JPN

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.

DOI： 10.5059/yukigoseikyokaishi.67.889

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年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/ol901236s

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年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/j.tetlet.2009.05.112

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年6月

記述言語：英語出版者・発行元：ELSEVIER SCIENCE SA

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.

DOI： 10.1016/j.ica.2008.12.033

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年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/jo900142b

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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 > 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 > 420 nm).

DOI： 10.1021/jp809119m

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

Yasushi Nishihara, Eiji Inoue, Yoshiaki Okada, Kentaro Takagi

SYNLETT ( 19 ) 3041 - 3045 2008年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：GEORG THIEME VERLAG KG

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.

DOI： 10.1055/s-0028-1087345

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年12月

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年5月

記述言語：英語出版者・発行元：JOHN WILEY & SONS INC

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.

DOI： 10.1002/pola.22671

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年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

[GRAPHICS]
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.

DOI： 10.1021/jo702103r

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

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 129 ( 42 ) 12634 - + 2007年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/ja075234y

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年7月

記述言語：英語出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/om700343y

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年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：SOC POLYMER SCIENCE JAPAN

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 (< 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.

DOI： 10.1295/polymj.PJ2006129

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年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ARKAT USA INC

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.

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 2007 ( 10 ) 29 - 48 2007年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Arkat

Treatment of 1,1,3,3-tetrakis(alkylthio)-2-silapropanes with t-BuLi in THF at -40°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. ©ARKAT-USA, Inc.

DOI： 10.3998/ark.5550190.0008.a05

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年10月

記述言語：英語出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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

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年10月

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年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

[GRAPHICS]
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.

DOI： 10.1021/ol060969d

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年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

[GRAPHICS]
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.

DOI： 10.1021/jo0520994

Preparation and polymerization of doubly functionalized polar norbornene derivatives

Yasushi Nishihara, Yoshiaki Inoue, Kentaro Takagi

Polymer Preprints, Japan 55 ( 1 ) 220 2006年

記述言語：日本語掲載種別：研究論文（国際会議プロシーディングス）

We have previously reported the palladium-catalyzed cyanoesterification of norbornene derivatives with ethyl cyanoformate. Herein we report that the same reaction of norbornadiene with various alkyl cyanoformates (alkyl = Me, Et, nPr, iPr, nBu, tBu, and Bn) can smoothly undergo to afford doubly polar functionalized norbornene derivatives. This reaction is a novel and efficient method to obtain a monomer having both cyano and ester groups with exo-selectivity. The formed norbornene derivatives were polymerized through ring-opening metathesis polymerization (ROMP) by the second generation Grubbs' catalyst. The results of gel permeation Chromatographic (GPC), thermogravimetric (TG), and differential scanning calorimeter (DSC) analyses of the obtained polymers will also be discussed.

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年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/j.tetlet.2005.10.056

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年11月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE BV

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

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年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：SPRINGER

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).

DOI： 10.1007/s11243-005-6408-x

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年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE SA

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

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年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：GEORG THIEME VERLAG KG

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

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

Pantcheva, I, Y Nishihara, K Osakada

ORGANOMETALLICS 24 ( 16 ) 3815 - 3817 2005年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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).

DOI： 10.1021/om049050t

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年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

[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).

DOI： 10.1246/bcsj.78.1469

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年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

DOI： 10.1246/bcsj.78.1288

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年6月

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年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

(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.

DOI： 10.1021/om049217i

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年11月

記述言語：英語出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/om049632a

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年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ROYAL SOC CHEMISTRY

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.

DOI： 10.1039/b315902g

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年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/om049922r

Syntheses of Dinuclear and Trinuclear Hydridoplatinum Complexes with Bridging Phosphido Ligands [Pt2H2(m-PR2)2(PEt3)2] (R = tBu, Ph) and [Pt3H2(m-PPh2)4(PEt3)2]. Characterization of the Triangular Intermediate [Pt3H(m-PPh2)3(PEt3)3] and Its Chemical Pr・・・

M. Itazaki, Y. Nishihara, K. Osakada

Organometallics 23 ( 7 ) 1610 - 1621 2004年3月

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年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ROYAL SOC CHEMISTRY

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.

DOI： 10.1039/b308741g

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：TAYLOR & FRANCIS LTD

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.

DOI： 10.1080/0095897031000069049

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年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/jo020293+

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年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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).

DOI： 10.1021/ic015630w

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

DOI： 10.1016/S0040-4039(02)00165-X

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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 > 7 > 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.

DOI： 10.1021/om010862o

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年11月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：NATL RESEARCH COUNCIL CANADA

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

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年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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).

DOI： 10.1246/cl.2001.950

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年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE SA

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

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年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE SA

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

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年5月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/om010081n

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年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

DOI： 10.1246/cl.2001.286

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

[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.

DOI： 10.1021/om010006c

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年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE SA

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.

DOI： 10.1016/S0022-328X(00)00794-4

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年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

[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.

DOI： 10.1021/ol0061586

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年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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.

DOI： 10.1021/jo000679p

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年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

DOI： 10.1246/bcsj.73.1409

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年4月

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年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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

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年3月

記述言語：英語出版者・発行元：AMER CHEMICAL SOC

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

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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

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年3月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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

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年2月

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年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

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

Palladium-catalyzed carbon-carbon bond-forming reactions of silanols. 査読

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

ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 218 U101 - U101 1999年8月

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

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

ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 218 U195 - U195 1999年8月

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年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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

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年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AMER CHEMICAL SOC

[GRAPHICS]
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

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年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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

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年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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 >99% yield. (C) 1999 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4020(99)00141-6

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年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：GEORG THIEME VERLAG

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.

A facile preparation and cyclopropanation of 1-alkenylsilanols 査読

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

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

記述言語：英語出版者・発行元：The Chemical Society of Japan

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

その他リンク： http://orcid.org/0000-0002-1163-264X

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

Nishihara Y, Ikegashira K, Mori A, Hiyama T

Tetrahedron Letters 39 ( 23 ) 4075 - 4078 1998年

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

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

Chemistry Letters 1998 ( 5 ) 443 - 444 1998年

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

Hirabayashi K, Nishihara Y, Mori A, Hiyama T

Tetrahedron Letters 39 ( 43 ) 7893 - 7896 1998年

Novel cage polycarbosilanes. Preparation and characterization of dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2]octane and its derivatives

Masaki Shimizu, Naoko Inamasu, Yasushi Nishihara, Tamejiro Hiyama

Chemistry Letters ( 11 ) 1145 - 1146 1998年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Chemical Society of Japan

2,2,3,3,5,5,6,6,7,7,8,8-Dodecamethyl-2,3,5,6,7,8-hexasilabicyclo[2.2.2] octane (1) was synthesized for the first time via three steps in 56% overall yield through triple silylation with three dichlorodimethyldisilane molecules of two trianionic molecules derived from bis(phenylthio)methane. The molecular structure of 1 was shown to be slightly distorted from an ideal bicyclo-[2.2.2]octane skeleton by X-ray analysis. The derivatization of 1 and UV spectra of those compounds are described.

DOI： 10.1246/cl.1998.1145

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

Yasushi Nishihara, Toyohisa Ishida, Shouquan Huo, Tamotsu Takahashi

Journal of Organometallic Chemistry 547 ( 2 ) 209 - 216 1997年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Elsevier

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

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

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

CHEMICAL COMMUNICATIONS ( 17 ) 1599 - 1600 1997年9月

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

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

TETRAHEDRON 53 ( 27 ) 9123 - 9134 1997年7月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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.

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

R Hara, Y Nishihara, PD Landre, T Takahashi

TETRAHEDRON LETTERS 38 ( 3 ) 447 - 450 1997年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD

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

Zirconocene catalyzed dehalogenation of aromatic halides by alkylmagnesium reagents 査読

R Hara, WH Sun, Y Nishihara, T Takahashi

CHEMISTRY LETTERS ( 12 ) 1251 - 1252 1997年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

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

Nishihara Y, Ikegashira K, Mori A, Hiyama T

Chemistry Letters 1997 ( 12 ) 1233 - 1234 1997年

記述言語：英語出版者・発行元：The Chemical Society of Japan

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

その他リンク： http://orcid.org/0000-0002-1163-264X

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

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

Chemical Communications ( 11 ) 1039 - 1040 1997年

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

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

Synlett ( 6 ) 693 - 694 1997年

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

Mori A, Fujita A, Nishihara Y, Hiyama T

Chemical Communications 1997 ( 22 ) 2159 - 2160 1997年

Highly selective monofunctionalization of zirconacyclopentanes and dialkylzirconocene complexes 査読

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

INORGANICA CHIMICA ACTA 252 ( 1-2 ) 91 - 99 1996年11月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ELSEVIER SCIENCE SA LAUSANNE

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.

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

T Takahashi, R Hara, Y Nishihara, M Kotora

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 118 ( 21 ) 5154 - 5155 1996年5月

High Yield Synthesis and Characterization of Chromaboranes. Comparison of the Geometric, Electronic, and Chemical Properties of an Electronically Unsaturated (.eta.5-C5Me5)2Cr2B4H8 Cluster with Its Saturated Derivative (.eta.5-C5Me5)2Cr2(CO)2B4H6 査読

Jianwei Ho, Kathryn J. Deck, Yasushi Nishihara, Maoyu Shang, Thomas P. Fehlner

Journal of the American Chemical Society 117 ( 41 ) 10292 - 10299 1995年10月

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

T TAKAHASHI, Y NISHIHARA, T ISHIDA

CHEMISTRY LETTERS ( 2 ) 159 - 160 1995年2月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：CHEMICAL SOC JAPAN

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.

Oxidative Addition of 2-Haloalkene to Zirconocene 査読

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

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

Preparation and Structure of (Cp*Cr)2B4H8. An Unsaturated Metallaborane Cluster with an Unexpected Structure 査読

Kathryn J. Deck, Yasushi Nishihara, Maoyu Shang, Thomas P. Fehlner

Journal of the American Chemical Society 116 ( 18 ) 8408 - 8409 1994年9月

Cluster chemistry driven by ligand bulk. Significance of the synthesis of nido-1-(.eta.5-C5Me5)Co-2-(.eta.4-C5Me5H)CoB3H8 and its dehydrogenation to nido-2,4-{(.eta.5-C5Me5)Co}2B3H7 査読

Yasushi Nishihara, Kathryn J. Deck, Maoyu Shang, Thomas P. Fehlner

Journal of the American Chemical Society 115 ( 25 ) 12224 - 12225 1993年12月

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