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

Abstract

Indirect electrolysis method using appropriate mediators enables numerous chemical reactions. The general principles of mediators were described herein with a particular focus on non‐transition metal mediators. Recent representative examples of bond formation reactions by indirect electrolysis are summarized and discussed here.

DOI： 10.1002/ejoc.202300835

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

DOI： 10.5796/electrochemistry.23-67078

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society of Japan  

DOI： 10.5796/electrochemistry.23-67079

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Publishing type：Research paper (scientific journal)  

DOI： 10.1149/MA2023-01412322mtgabs

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

DOI： 10.1021/acs.orglett.3c01914

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

Electrochemical dehydrogenative C-O bond formation for the synthesis of sultones was achieved. In the presence of K2CO3 and H2O, constant current electrolysis of [1,1'-biphenyl]-2-sulfonyl chloride afforded an aryl-fused sultone quantitatively. Under the optimized conditions, a variety of sultone derivatives were obtained. Control experiments suggest that the electrochemical oxidation of the sulfonates generated in situ would afford sulfo radical intermediates.

DOI： 10.1021/acs.orglett.3c01062

PubMed

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Authorship：Lead author,　Corresponding author   Language：English   Publishing type：Research paper (scientific journal)   Publisher：Georg Thieme Verlag KG  

Abstract

An electrochemical cross-coupling reaction between arylboronic esters and aryllithiums was developed. The presence of Br– in the electrolyte was found to be essential for the reaction. NaBr was chosen as the electrolyte for its inexpensiveness and abundance, and also acted as a halogen mediator. The reaction proceeded under mild conditions to afford biaryls.

DOI： 10.1055/a-2034-9821

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Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.oprd.2c00267

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

DOI： 10.1021/acs.orglett.2c03574

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/cl.220368

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Authorship：Lead author   Publishing type：Research paper (scientific journal)   Publisher：Beilstein Institut  

Electrochemical hydrogenation of enones using a proton-exchange membrane reactor is described. The reduction of enones proceeded smoothly under mild conditions to afford ketones or alcohols. The reaction occurred chemoselectively with the use of different cathode catalysts (Pd/C or Ir/C).

DOI： 10.3762/bjoc.18.107

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Other Link： https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-18-107.pdf

Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

Five triphenyltriphenylamines with various substituents were investigated as precursors for near-infrared absorbing materials. Cyclic voltammetry (CV) studies showed that they all give stable radical cations in solution. The radical cations obtained by one-electron chemical oxidation of these compounds show strong absorption in the near-infrared region, and the position of the absorption is strongly influenced by the substituent. DFT (density functional theory) calculations suggest that the introduction of stronger electron-donating substituents would result in a smaller HOMO–SOMO energy gap and thus a larger long wavelength shift, which is consistent with the experimental results. On the other hand, strong electron-withdrawing substituents increase the HOMO–SOMO energy gap, resulting in a short wavelength shift. The position of the near-infrared absorption peak of the triphenylamine radical cation can be controlled to the longer or shorter wavelength direction depending on the substituent. A molecular design of near-infrared absorbing dyes utilizing the electronic effects of substituents is described.

DOI： 10.3390/colorants1030021

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Publishing type：Research paper (scientific journal)  

DOI： 10.1149/MA2022-01421838mtgabs

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DOI： 10.1149/MA2022-01421832mtgabs

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/cl.220112

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Publishing type：Research paper (scientific journal)  

DOI： 10.3390/colorants1020014

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

Cyanosilylation of carbonyl compounds provides protected cyanohydrins, which can be converted into many kinds of compounds such as amino alcohols, amides, esters, and carboxylic acids. In particular, the use of trimethylsilyl cyanide as the sole carbon source can avoid the need for more toxic inorganic cyanides. In this paper, we describe an electrochemically initiated cyanosilylation of carbonyl compounds and its application to a microflow reactor. Furthermore, to identify suitable reaction conditions, which reflect considerations beyond simply a high yield, we demonstrate machine learning-assisted optimization. Machine learning can be used to adjust the current and flow rate at the same time and identify the conditions needed to achieve the best productivity.

DOI： 10.1021/acs.joc.1c01242

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Elsevier BV  

DOI： 10.1016/j.dyepig.2021.109929

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

DOI： 10.1002/tcr.202100033

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Other Link： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/tcr.202100033

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

The first Cu-catalyzed dehydrogenative C-O cyclization for the synthesis of furan-fused thienoacenes is described. A variety of heteroacenes including a thieno[3,2-b]furan or a thieno[2,3-b]furan skeleton were synthesized by intramolecular C-H/O-H coupling. The use of a mixed solvent of N-methyl-2-pyrrolidone, ethylene glycol monomethyl ether, and toluene was essential for suppressing side reactions and efficiently promoting the reaction. Double C-O cyclization was also conducted to afford highly π-expanded furan-fused thienoacenes.

DOI： 10.1021/acs.orglett.1c01256

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PubMed

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Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/cl.200809

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

DOI： 10.1021/acs.orglett.0c03956

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

<p>4,4′-Bibenzo[<italic>c</italic>]thiophene <bold>4,4′-BBT</bold> and its silyl-substituted derivatives <bold>1,1′-Si-4,4′-BBT</bold> and <bold>1,1′,3,3′-Si-4,4′-BBT</bold> have been designed and developed as new π-building blocks.</p>

DOI： 10.1039/d1ra01189h

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Publishing type：Research paper (scientific journal)  

An efficient enantioselective acylative desymmetrization of glycerol was developed by using a chiral DMAP derivatives 1e having a 1,1-binaphthyl unit. The reactions required only 0.1 mol% of the catalyst and showed moderate to good enantioselectivity (up to 94:6 er). Control experiments revealed that the first acylation of a glycerol derivative proceeded selectively rather than the second acylation to give diacylate.

DOI： 10.3987/COM-21-14433

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

A one-pot procedure for the synthesis of thienyl thioethers is described. Several thienyl thioethers were synthesized by a TfOH-promoted Friedel-Crafts-type cyclization, a subsequent nucleophilic attack by an arenethiol, and dehydration. This protocol was successfully applied to the synthesis of thienoacene derivatives by using a Pd-catalyzed dehydrogenative cyclization.

DOI： 10.1055/s-0040-1707280

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Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society  

DOI： 10.1149/MA2020-02432766mtgabs

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：International Union of Crystallography (IUCr)  

In the title molecule, C₄₈H₃₃N, the central N atom shows no pyramidalization, so that the N atom and the three C atoms bound to the N atom lie almost in the same plane. The three <italic>para</italic>-phenylene rings bonded to the N atom are in a propeller form. All of the naphthalene ring systems are slightly bent. In the crystal, molecules form an inversion dimer, through two pairs of C—H...<italic>π</italic> interactions, which further interacts with the adjacent dimer <italic>via</italic> another two pairs of C—H...<italic>π</italic> interactions, forming a column structure along the <italic>a</italic> axis. There are no significant interactions between these column structures.

DOI： 10.1107/s2056989020012529

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

DOI： 10.1246/cl.200161

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Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/ange.202001149

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Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society  

DOI： 10.1149/MA2020-01432507mtgabs

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Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society  

DOI： 10.1149/MA2020-01432489mtgabs

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

A 1,10-phenanthroline-promoted cyanation of aryl iodides has been developed. 1,10-Phenanthroline worked as an organocatalyst for the reaction of aryl iodides with tetraalkylammonium cyanide to afford aryl cyanides. A similar reaction occurred through an electroreductive process.

DOI： 10.1055/s-0037-1611793

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

The first synthesis of dithieno-1,2-oxaborine derivatives was achieved via iodide-mediated or iodide-catalyzed demethylation of 3-methoxy-2,2'-bithiophene and subsequent C-H borylation. A wide variety of thiophene-fused oxaborines could be synthesized by the procedure.

DOI： 10.1021/acs.orglett.9b00485

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

An efficient enantioselective acyl migration reaction of furanyl carbonates was developed to construct all-carbon quaternary stereogenic centers. In some cases, the reactions required only 0.05 mol% (minimum 500 ppm) of catalyst and showed a high turnover frequency value (TOF; 3640 h(-1)). Multigram-scale reactions (10 grams) also proceeded with high enantioselectivity (> 99:1 e.r.) in quantitative yield. The catalyst was robust and easily recovered in 98% yield. A wide range of functional groups were tolerated (15 examples, > 98% yield, up to > 99:1 e.r.), and a variety of optically active 3,3'-disubstituted benzofuranone derivatives, which are useful intermediates for the synthesis of natural products and pharmaceuticals, were efficiently obtained. Control experiments on the catalyst structure (e.g., catalyst 1 a vs. 1 a' and 1 a") and computational calculations revealed that both the catalytic activity and enantioselectivity should be enhanced by hydrogen bonding between catalyst and substrate. Moreover, this system was applied to the challenging gamma-selective acyl migration reaction of furanyl carbonates with high gamma-selectivity and high enantioselectivity (a:gamma=10:90, 95:5 e.r.).

DOI： 10.1002/chem.201806050

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

We developed an enantioselective desymmetrization of 1,3-diols by a chiral N,N-dimethyl-4-aminopyridine (DMAP) derivative containing a 1,1'-binaphthyl with tert-alcohol units. The reactions required only 0.1 mol % of catalyst and showed moderate to high chemoselectivity (monoacylation vs. diacylation) and enantioselectivity (14 examples, up to 95:5 er). Several control experiments revealed that diol units in both the substrate and the catalyst are important to achieve high enantioselectivity.

DOI： 10.1246/cl.180697

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

The first synthesis of dithieno[3,2-b:2',3'-e][1,4]azaborinine (DTAB) derivatives has been achieved by Buchwald-Hartwig coupling and subsequent Friedel-Crafts-type C-H borylation. A facile method for further pi-extension of DTAB was also developed via stannylation and subsequent Kosugi-Migita-Stille cross-coupling reaction. The fundamental properties of DTAB derivatives were also investigated.

DOI： 10.1021/acs.orglett.8b03316

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Publishing type：Research paper (scientific journal)   Publisher：Wiley  

DOI： 10.1002/ajoc.201800367

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

A dynamic kinetic resolution (DKR) of azlactones in the presence of benzoic acid and a binaphthyl-based N,N-4-dimethylaminopyridine (DMAP) derivative 1i having two amide groups at the 3,3'-positions of a binaphthyl unit is developed. The reaction proceeded smoothly with a wide range of azlactones to provide alpha-amino acid derivatives with good to high enantiomeric ratios (er's). A multigram-scale reaction (2.5 g) for the DKR of azlactone 2d was also demonstrated, and the resulting product was converted to unnatural alpha-amino acid 6d'.

DOI： 10.1021/acs.orglett.8b01960

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

Efficient syntheses of benzodithienofuran (BDTF; [1]benzothieno[3,2-b]thieno[2,3-d]furan) and benzodithienothiophene (BDTT; [1]benzothieno[3,2-b]thieno[2,3-d]thiophene) were achieved by the combination of an addition-elimination reaction, reduction, and Pd-catalyzed dehydrogenative cyclization. We also achieved the synthesis of pi-ex- tended BDTF and BDTT derivatives through the use of coupling reactions. The detailed physical properties of these compounds were investigated. The newly synthesized BDTFs exhibited strong fluorescence compared with BDTTs. 2,2'-Bis([1]benzothieno[3,2-b]thieno[2,3-d]furan) (BBTTF) exhibited p-type organic field-effect transistor (OFET) properties.

DOI： 10.1002/ajoc.201800270

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Authorship：Lead author   Language：English   Publisher：American Chemical Society  

Recent advances in electro-organic chemistry involving miniaturization, integration, and combinatorial chemistry were reviewed. Microelectrode array technology for site-selective electro-organic reactions and addressable libraries provides a direct and unlabeled method for measuring small-molecule-protein interactions. Electrochemical systems using solid-supported bases and acids ("site separation") can realize electrolysis without the addition of supporting electrolytes. Well-designed "bipolar electrodes" have enabled the production of patterned gradient polymer brushes and microfibers. For the display of combinatorial organic electrochemistry, batch and flow electrolysis systems for the optimization and screening of electro-organic reactions as well as the building of chemical libraries for organic compounds are described.

DOI： 10.1021/acs.chemrev.7b00532

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：The Chemical Society of Japan  

Cu/Fe-cocatalyzed cross-coupling reactions between 3-bromobenzo[b]thiophene and hydroxyaryls are described herein. The combination of Cu and Fe catalysts is important for the progress of the reactions, and the use of triphenylphosphine oxide as a ligand suppresses the dehalogenation of 3-bromobenzo[b]thiophene, and promptly facilitates the reaction. The obtained aryl benzo[b]thienyl ethers can be converted to pextended thienobenzofuran derivatives via Pd-catalyzed dehydrogenative cyclizations.

DOI： 10.1246/cl.180425

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Beilstein-Institut Zur Forderung der Chemischen Wissenschaften  

In this study, six-membered N-acyliminium ions were generated by the “indirect cation pool” method and reacted with several nucleophiles. These reactions afforded disubstituted piperidine derivatives with high diastereoselectivities and good to excellent yields. The conformations of the obtained N-acyliminium ions were studied by low temperature NMR analyses and DFT calculations and were found to be consistent with the Steven’s hypothesis.

DOI： 10.3762/bjoc.14.100

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Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society  

DOI： 10.1149/MA2018-01/34/2029

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Language：English   Publisher：Elsevier B.V.  

In this study, recent advances in electro-organic chemistry based on combinatorial approaches are reviewed. As examples of combinatorial organic electrosynthesis, some batch and flow electrolysis systems for the screening and optimization of electro-organic reactions are described along with the construction of chemical libraries of organic compounds.

DOI： 10.1016/j.coelec.2017.10.026

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

The reaction of silyl dienol ether of gamma-pyrone with dimethyl acetylenedicarboxylate (DMAD) gives the regioselective insertion product in 66% yield. This DMAD-insertion reaction is thought to include a three-step sequence: (1) thermal [2+2]-type cycloaddition reaction of silyl dienol ether of gamma-pyrone with DMAD, (2) ring-opening electrocyclic reaction of the cyclobutene skeleton, and (3) hydrolysis of the silyl dienol ether. The present reaction proceeds under mild conditions without any catalysts or heating. In addition, the [2+2]-type cycloaddition reaction proceeds regioselectively at the C3-C4 double bond in the silyl dienol ether of gamma-pyrone.

DOI： 10.3987/COM-17-13820

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

An extremely efficient acylative kinetic resolution of d,l-1,2-diols in the presence of only 0.5 mol% of binaphthyl-based chiral N,N-4-dimethylaminopyridine was developed (selectivity factor of up to 180). Several key experiments revealed that hydrogen bonding between the tert-alcohol unit(s) of the catalyst and the 1,2-diol unit of the substrate is critical for accelerating the rate of monoacylation and achieving high enantioselectivity. This catalytic system can be applied to a wide range of substrates involving racemic acyclic and cyclic 1,2-diols with high selectivity factors. The kinetic resolution of d,l-hydrobenzoin and trans-1,2-cyclohexanediol on a multigram scale (10 g) also proceeded with high selectivity and under moderate reaction conditions: (i) very low catalyst loading (0.1 mol%); (ii) an easily achievable low reaction temperature (0 degrees C); (iii) high substrate concentration (1.0M); and (iv) short reaction time (30 min).

DOI： 10.1002/adsc.201700057

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

We developed an acylative desymmetrization of meso-1,2-diols using a binaphthyl-based N,N-4-dimethylamino-pyridine (DMAP) derivative lh with tert-alcohol substituents. The reaction proceeds with a wide range of acyclic meso-1,2-diols and six-membered-ring meso-1,2-diols to provide a monoacylate selectively with a high enantiomeric ratio (er). Only 0.1 mol % of the catalyst facilitated the reaction within a short reaction time (3 h) to afford enantio-enriched monoacylated products in moderate to good yield. Several control experiments revealed that the tert-alcohol units of catalyst lh play a significant role in achieving high catalytic activity, chemoselectivity of monoacylation, and enantioselectivity.

DOI： 10.1021/acs.joc.7b00992

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The synthesis of 3-benzo[b]thienyl 3-thienyl ether and its dehydrogenative cyclization leading to benzodithienofuran (BDTF; [1]benzothieno[3,2-b]thieno[2,3-d]furan) are described for the first time. Further transformation of BDTF to more p-extended BDTF derivatives and their fundamental physical properties are also studied.

DOI： 10.1021/acs.orglett.7b00969

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Straightforward syntheses leading to pi-extended benzosilolothiophene (BST) derivatives by Rh-catalyzed dehydrogenative cyclization reactions have been developed. Electron-deficient ligands were effective for the reactions, and dppe-F-20 gave the best result. This method could be applied to the synthesis of highly pi-extended ladder-type BST derivatives, which exhibited fluorescence.

DOI： 10.1021/acs.orglett.7b00878

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Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society  

DOI： 10.1149/MA2017-01/36/1700

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

We have developed an intramolecular nucleophile-catalyzed aldol-lactonization (NCAL) reaction of S-aryl-(E)-6-oxohex-2-enethiolate with N,N-4-dimethylaminopyridine N-oxide (DMAPO) to afford densely functionalized bicyclic beta-lactones in moderate yield. This unique transformation may be explained in terms of nucleophilic substitution of the S-aryl moiety by DMAPO, followed by 1,4-addition of aryl thiolate to generate a zwitterionic enolate and an intramolecular C-C bond-forming reaction (aldol-lactonization).

DOI： 10.3987/COM-16-13614

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Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1021/acs.orglett.7b00969

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：GEORG THIEME VERLAG KG  

Facile synthetic methods for constructing naphthothiophenone and its -extended derivatives were developed. Naphthothiophenone and anthradithiophenedione were synthesized by the S-acylation of thiol to form chlorothioformate and subsequent Friedel-Crafts acylation. A bromination reaction of naphthothiophenone and its application to Suzuki-Miyaura cross-coupling was also carried out. The fundamental physical properties of these compounds were also investigated.

DOI： 10.1055/s-0035-1562470

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

We developed an acylative kinetic resolution of secondary carbinols using a binaphthyl-based N,N-4-dimethylaminopyridine (DMAP) derivative 1d with tert-alcohol substituents. The reaction proceeded with a wide range of carbinols with moderate to high selectivity (s) (up to s = 79.5). Kinetic studies revealed that catalyst 1d was more catalytically active than the corresponding bis-methyl ether 1d' or DMAP. Hydrogen bonding between tert-alcohols of the catalyst and secondary carbinols was responsible for the enhanced reaction rate and high enantioselectivity.

DOI： 10.1246/bcsj.20160135

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Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society  

DOI： 10.1149/MA2016-01/32/1617

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DOI： 10.1149/MA2016-01/32/1590

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：NATURE PUBLISHING GROUP  

Catalysts that can promote acyl transfer processes are important to enantioselective synthesis and their development has received significant attention in recent years. Despite noteworthy advances, discovery of small-molecule catalysts that are robust, efficient, recyclable and promote reactions with high enantioselectivity can be easily and cost-effectively prepared in significant quantities (that is, &gt;10 g) has remained elusive. Here, we demonstrate that by attaching a binaphthyl moiety, appropriately modified to establish H-bonding interactions within the key intermediates in the catalytic cycle, and a 4-aminopyridyl unit, exceptionally efficient organic molecules can be prepared that facilitate enantioselective acyl transfer reactions. As little as 0.5 mol% of a member of the new catalyst class is sufficient to generate acyl-substituted all-carbon quaternary stereogenic centres in quantitative yield and in up to 98: 2 enantiomeric ratio (er) in 5 h. Kinetic resolution or desymmetrization of 1,2-diol can be performed with high efficiency and enantioselectivity as well.

DOI： 10.1038/ncomms11297

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Bis(diaryl)-1,3-butadiynes bearing two amino moieties were easily synthesized by a sequential coupling reaction by using an electrochemical method. This sequential reaction consists of electrochemical oxidative homocoupling and Suzuki-Miyaura coupling. The fluorescence of the obtained bis(diaryl)-1,3-butadiynes is solvatochromic despite their symmetric linear structure and lack of a strong acceptor moiety.

DOI： 10.1002/ajoc.201500502

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Iron oxide produced by iron-oxidizing bacteria, Leptothrix ochracea, (L-BIOX) obtained from a freshwater purification plant, Joyo City in Kyoto, Japan catalyzed Baeyer-Villiger oxidation with molecular oxygen in the presence of benzaldehyde at 25 degrees C more efficiently than usual iron compounds. L-BIOX can promote the reactions of various substrates to give the desired products in sufficient yields and was found to be reusable. Scanning transmission electron microscopy and Fe-57 Mossbauer spectroscopy revealed that no change of the surface structure of L-BIOX was observed even after four times of the recycling test and the oxidation state of iron in L-BIOX is trivalent before and after the oxidation of cyclohexanone. An investigation with analogous amorphous iron oxides which contain silicon revealed that the catalytic activity of L-BIOX might stem from a synergetic effect of iron and silicon in the structure. (C) 2015 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2015.10.057

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A method for the facile synthesis of ethene-bridged terthiophenes (EBTTs) in two steps has been developed. The first step is a double Sonogashira coupling between 3',4'-dibromo-2,2':5',2 ''-terthiophene and terminal alkynes to give dialkynylated terthiophenes, and the second step is a cyclization reaction to afford EBTTs. The fundamental physical properties of EBTTs were also studied.

DOI： 10.1021/acs.orglett.5b02417

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Chiral N,N-4-(dimethylamino)pyridine (DMAP) derivatives, which can be readily prepared by the Ugi multicomponent reaction in a one-pot manner, have been efficiently applied to the enantioselective Steglich rearrangement of oxindole derivatives to give the desired products bearing a quaternary carbon center in high yield (&gt;98% yield) and with high enantioselectivity (up to 99:1 er).

DOI： 10.1021/acs.orglett.5b02089

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Palladium-catalyzed domino CH/NH functionalization for the synthesis of novel nitrogen-bridged thienoacenes and 10H-benzo[4,5]thieno[3,2-b]indole derivatives from dihaloarene is reported. This domino sequence consists of initial CH functionalization of the benzo[b]thiophene moiety, followed by Buchwald-Hartwig coupling. This transformation is also useful for the synthesis of highly -extended compounds.

DOI： 10.1002/chem.201500897

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Language：Japanese   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

An electrochemical method to synthesize cationic palladium complexes has been developed. Their counter anions could be changed readily by the electrolyte. The reaction could be incorporated into electro-oxidative palladium catalyzed reactions, such as Wacker-type reaction, homo-coupling of arylboronic acids, oxidative Sonogashira-type coupling, and Glaser-type coupling of terminal alkynes. These reactions exhibited a wide scope and a variety of products were obtained in high yields due to high activity of electrogenerated palladium species. We also developed site-selective sequential reactions by the integration of the electro-oxidative coupling reactions with non-electrochemical reactions. The reaction site could be controlled completely by the on/off application of electricity.

DOI： 10.5059/yukigoseikyokaishi.73.171

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Language：English   Publisher：The Electrochemical Society of Japan  

DOI： 10.5796/electrochemistry.83.477

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Other Link： https://jlc.jst.go.jp/DN/JLC/20011551902?from=CiNii

Language：Japanese   Publisher：Society of Synthetic Organic Chemistry  

An electrochemical method to synthesize cationic palladium complexes has been developed. Their counter anions could be changed readily by the electrolyte. The reaction could be incorporated into electro - oxidative palladium catalyzed reactions, such as Wacker-type reaction, homo -coupling of arylboronic acids, oxidative Sonogashira-type coupling, and Glaser - type coupling of terminal alkynes. These reactions exhibited a wide scope and a variety of products were obtained in high yields due to high activity of electrogenerated palladium species. We also developed site-selective sequential reactions by the integration of the electro - oxidative coupling reactions with non - electrochemical reactions. The reaction site could be controlled completely by the onloff application of electricity.

DOI： 10.5059/yukigoseikyokaishi.73.171

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：GEORG THIEME VERLAG KG  

Optically active polyhydroxy trans-1,2-amino alcohols were efficiently synthesized in good to excellent yields by the Petasis boronic-Mannich reaction of an amine, an organoboronic acid, and a chiral lactol, which was prepared from D-araboascorbic acid or its diastereomer. Further transformations of the resulting Petasis products were investigated in detail to obtain chiral building blocks containing three continuous stereogenic centers.

DOI： 10.1055/s-0034-1378900

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Interleukin (IL)-6 is a proinflammatory cytokine that performs a wide variety of biological functions, including important roles in the progression of chronic inflammatory diseases such as periodontal disease. (+)-Terrein, a secondary bioactive fungal metabolite isolated from Aspergillus terreus, has various biological activities; however, its anti-inflammatory effects are still unknown. The purpose of this study was to examine the effect of synthetic (+)-terrein on IL-6 signaling and related protein production in human gingival fibroblasts. To our knowledge, this study is the first to report that synthetic (+)-terrein is not cytotoxic at concentrations less than 20 mu M and suppresses IL-6/soluble IL-6 receptor (sIL-6R)-induced phosphorylation of signal transducer and activator of transcription-3, extracellular signal-regulated kinase 1/2, and c-jun N-terminal kinase 1/2-signaling proteins that are downstream of IL-6 signaling. In addition, synthetic (+)-terrein suppresses IL-6/sIL-6R-induced vascular endothelial growth factor (VEGF) secretion in a concentration-dependent manner (p &lt; 0.01). These data suggest that synthetic (+)-terrein has potential anti-IL-6 signaling activity and suppresses VEGF-associated inflammatory disease progression. (C) 2014 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.bmc.2014.07.047

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

The rate of the intramolecular Morita-Baylis-Hillman (MBH) reaction is remarkably enhanced by the combination of catalytic amounts of a nucleophilic catalyst (4-dimethylaminopyridine (DMAP), 4-pyrrolidinopyridine (PPY), or PBu3) and 1,3-diphenyl-2-thiourea, and the desired MBH adducts are obtained in good to high yields within a few hours.

DOI： 10.1002/ajoc.201402001

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELECTROCHEMICAL SOC JAPAN  

An electro-reductive halogen-deuterium exchange reaction in CD3CN has been developed. Using 9-fluorenone as a mediator, the electro-reduction of several aryl halides proceeded smoothly to give the deuterated products selectively. A methylation reaction of aryl halides also proceeded under similar conditions. (C) The Electrochemical Society of Japan, All rights reserved.

DOI： 10.5796/electrochemistry.81.362

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELECTROCHEMICAL SOC JAPAN  

Electro-oxidative Wacker-type reaction has been developed in PEG/CH3CN thermomorphic biphasic system. The heterogeneous solution was turned into homogeneous solution with heating to 60 degrees C, and electro-oxidative Wacker-type reactions of alkenes bearing long alkyl chains proceeded smoothly to afford methyl ketones in good yields. The recycling of PEG phase containing Pd has also been achieved. (C) The Electrochemical Society of Japan, All rights reserved.

DOI： 10.5796/electrochemistry.81.347

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Language：English   Publishing type：Research paper (scientific journal)  

The first synthesis of hexa(furan-2-yl)benzene derivatives is described. The RhCl3/i-Pr2NEt-catalyzed cyclotrimerization of di(furan-2-yl)acetylenes was an effective method for constructing hexa(furan-2-yl)benzene derivatives in good yields. Their π-extended derivatives were also synthesized by Suzuki-Miyaura coupling between hexakis(5-Bpinfuran-2-yl)benzene (Bpin = (pinacolato)boryl) and several aryl iodides. © 2013 American Chemical Society.

DOI： 10.1021/jo302652r

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Language：English   Publishing type：Research paper (scientific journal)  

The kinetic resolution of secondary alcohols was examined by new chiral DMAP derivatives, which can readily be prepared by the Ugi multicomponent reaction in a one-pot operation. The initial screening of DMAP derivatives indicated that the catalyst bearing L-valine with an S configuration at the a-position of amide showed the best stereoselectivity factor. After the reaction conditions were optimized with (S,S)-4a in the kinetic resolution of secondary alcohols, various acyclic and cyclic secondary alcohols could be resolved with an s -factor of up to 12. © 2013 The Japan Institute of Heterocyclic Chemistry.

DOI： 10.3987/COM-12-12624

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

In the presence of fluorene derivatives, the electro-reduction of aryl chlorides, bromides, and iodides bearing an ethylene moiety proceeded smoothly to afford the corresponding cyclized products. Noteworthy is that aryl chlorides, which have more negative reduction potential than aryl bromides and iodides, exhibited high reactivity in the reaction, and the corresponding five-membered and six-membered cyclized products were obtained in good to high yields. Mechanistic study suggests that the electro-reduction of fluorene derivatives was essential for the reactions, indicating that they work as a mediator. (C) 2012 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.electacta.2012.03.130

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

An efficient and simple protocol for the kinetic resolution of secondary alcohols is presented. The new system is based on a combination of chiral Bronsted acid, DABCO, and acetyl chloride and gives various enantioenriched alcohols with selectivity factors up to 105.

DOI： 10.1021/ol301373x

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The first synthesis of nitrogen-bridged terthiophenes (NBTTs) has been achieved by a tandem Buchwald-Hartwig coupling of 3,3',3 '', 4'-tetrabromo-2,2':5',2 ''-terthiophene. Several NBTT derivatives bearing aryl or alkyl moieties on the N-atoms could be synthesized. Their fundamental electrochemical characteristics and HOMO-LUMO levels were found to be influenced by the substituents on the N-atoms.

DOI： 10.1021/ol300887t

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Site-selective sequential coupling reactions directed toward bis(diaryl)butadiynes are described. The reaction site could be controlled completely by the on/off application of electricity. The electro-oxidative homo-coupling of terminal alkynes (electricity ON) and the subsequent Suzuki-Miyaura coupling (electricity OFF) afforded bis(diaryl) butadiynes in high yields. The obtained 1,4-bis(diaryl)butadiynes could be converted to a 2,5-bis(diaryl)thiophene derivative, which exhibited blue fluorescence.

DOI： 10.1039/c2ob26567b

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

Diastereoselective Ugi reactions of DMAP-based aldehydes with alpha-amino acids and tert-butyl isocyanide were examined. The reactions of 4-(dimethylamino)-2-pyridine-carboxaldehyde with various alpha-amino acids afforded 2-substituted DMAP derivatives with low diastereoselectivity. On the contrary, reactions with 4-(dimethylamino)-3-pyridine-carboxaldehyde delivered 3-substituted DMAP derivatives with moderate to high diastereoselectivity. The combination of alpha-amino acid and DMAP-based aldehyde is thus important to achieve high diastereoselectivity. Kinetic resolution of a secondary alcohol using a chiral DMAP derivative obtained through these reactions was also examined.

DOI： 10.3390/molecules16108815

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Carbene ligands bearing a pyridyl group and an ethylenedioxyl moiety were developed, and utilized as efficient ligands for the nickel-catalyzed Kumada-Tamao-Corriu coupling. A wide variety of aryl chlorides could be used for the cross-coupling reaction with aryl Grignard reagents to afford the corresponding products in high yields in short time.

DOI： 10.1246/cl.2011.936

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Publishing type：Research paper (scientific journal)   Publisher：Wiley-Blackwell  

DOI： 10.1002/chin.200239250

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DOI： 10.1002/chin.200212082

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DOI： 10.1002/chin.201004086

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

An electro-oxidative method for generating silver acetylides from acetylenes with a Ag anode was developed. The reaction could be integrated into a Pd-catalysed electrochemical Sonogashira-type reaction. In the presence of the catalytic amount of Pd(OAc)(2) and 4-BzO-TEMPO, electro-generated silver acetylides reacted immediately with arylboronic acids to afford the corresponding coupling adducts in high yields.

DOI： 10.1039/c0cc02633f

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

An electro-oxidative method for generating silver acetylides from acetylenes with a Ag anode was developed. The reaction could be integrated into a Pd-catalysed electrochemical Sonogashira-type reaction. In the presence of the catalytic amount of Pd(OAc)(2) and 4-BzO-TEMPO, electro-generated silver acetylides reacted immediately with arylboronic acids to afford the corresponding coupling adducts in high yields.

DOI： 10.1039/c0cc02633f

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELECTROCHEMICAL SOC JAPAN  

Halide ion-promoted desulfo-halogenation was applied successfully to synthesis of 4-chloro-2-azetidinone 1, a potent intermediate for carbapenem synthesis. and stereoselective N-glycosylation of 2,3-deoxyglycosides. Bromide ion/N-oxyl compounds (TEMPO) double mediatory systems enabled us to develop several aqueous electrolysis media free from organic solvents, e.g., silica gel or polymer particles/water disperse systems and water-soluble TEMPO-mediated oil-in-water emulsion systems, in which electrooxidation of alcohols was carried out successfully in a simple beaker-type undivided cell under a constant current condition. Notably, the work-up process was very simple and the solid particles (disperse phase) and the aqueous solutions (disperse media) were easily recovered and reused, offering a totally closed system. In Pd(OAc)(2)/TEMPO double mediatory systems, electrogeneration of active cationic palladium catalysts was integrated into electrooxidative Wacker-type reaction. In a similar manner, Wacker-type cyclization and homo-coupling of arylboronic acids were successfully achieved.

DOI： 10.5796/electrochemistry.77.1002

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Novel long-chain dialkyl fluorene-9,9-dicarboxylates were synthesized by treating fluorene with lithium diisopropylamide followed by alkyl chloroformates. The fluorene derivatives were readily electro-oxidized to form electroactive films on the Surface of a glassy carbon electrode. From the viewpoint of suitable potential window (from -2.5 to 1.5 V vs Ag/Ag(+)), cyclic voltammograms of the films indicated the electroactive properties of the fluorene derivatives that make them good candidates for electrochemical capacitor materials. (C) 2009 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2009.08.052

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

A facile electrooxidative method for synthesizing biaryls from arylboronic acids or arylboronic esters is described. In the presence of a catalytic amount of Pd(OAC)(2) and TEMPO, the electrooxidation of arylboronic acids or arylboronates gave the corresponding biaryls in moderate to excellent yields. (C) 2009 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2009.08.004

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELECTROCHEMICAL SOC JAPAN  

Palladium/2,2,6,6-tetramethylpiperidine-1-oxyl (Pd/TEMPO) double-mediatory electrooxidative Wacker-type cyclization of 1 was developed. In a mixture solution of dioxane and water, the reaction efficiently proceeded at room temperature to give benzofuran derivative 2.

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Nickel pincer complex 1 was prepared by the treatment of nickel pincer 2 with AgBF(4). Cationic nickel pincer complex 1 was air-stable and easy to handle, and was successfully applied to Michael addition and Mizoroki-Heck reaction. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.10.029

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

An electrochemical method for generating cationic palladium complexes was integrated into an electrooxidative homo-coupling of arylboronic acids. In the presence of a catalytic amount of-TEMPO, the homo-Coupling reaction proceeded efficiently under argon to afford symmetric biaryls. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.09.022

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

The RhCl(3)-3H(2)O/i-Pr(2)NEt-catalyzed [2+2+2] cyclotrimerization of alkynes has been achieved. The reaction can be widely used for various alkynes and provides tri- OF hexa-substituted benzenes regioselectively in high yields. The [2+2+2] cycloaddition of diynes and alkynes is also developed, and it affords benzene derivatives in moderate to high yields. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2008.03.079

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Publishing type：Research paper (scientific journal)   Publisher：Wiley-Blackwell  

DOI： 10.1002/chin.200814085

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

In the presence of RhCl(3)center dot 3H(2)O and i-Pr(2)NEt, the cyclotrimerization of di(2-thienyl)acetylenes proceeded smoothly to afford hexa(2-thienyl)benzenes. CV analysis of the hexa(2-thienyl)benzenes showed that they may be useful as electroactive materials. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.02.069

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

In the presence of RhCl(3)center dot 3H(2)O and i-Pr(2)NEt, the cyclotrimerization of di(2-thienyl)acetylenes proceeded smoothly to afford hexa(2-thienyl)benzenes. CV analysis of the hexa(2-thienyl)benzenes showed that they may be useful as electroactive materials. (C) 2008 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2008.02.069

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DOI： 10.1002/chin.200801025

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Publishing type：Research paper (scientific journal)   Publisher：The Electrochemical Society of Japan  

DOI： 10.5796/electrochemistry.76.859

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Electrooxidation of alcohols in water with water-soluble N-oxyl derivatives bearing a sulfonic acid group (anionic WS-TEMPOs) as a mediator proceeded to afford the corresponding ketones and aldehydes in moderate to good yields. The aqueous solution containing WS-TEMPOs could be readily recovered and reused for the electrooxidation of alcohols, thereby providing a totally closed system. (c) 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2007.10.088

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

RhCl3/amine was found to be an efficient catalyst for the cyclotrimerization of alkynes. The [2 + 2 + 2] cyclotrimerization of internal alkynes proceeded smoothly to afford hexa-substituted benzenes regioselectively in moderate to high yields.

DOI： 10.1246/cl.2007.998

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DOI： 10.1002/chin.200725042

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

We have developed an electrooxidative method for generating cationic palladium complexes [Pd(CH3CN)(4)][X](2) (X = BF4, PF6, and ClO4) from Pd(OAc)(2) and several electrolytes bearing X groups in CH3CN. The system could be integrated into an electrochemical Wacker-type reaction. In the presence of a catalytic amount of TEMPO, the reaction proceeded smoothly to give the corresponding methyl ketones.

DOI： 10.1021/ja069043r

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DOI： 10.1002/chin.200702104

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELECTROCHEMICAL SOC JAPAN  

Electropolymerization of 9,9-dialkylfluorenes (R(n)fluo, n: number of carbons in the chain) with long normal alkyl chains (n = 4, 5, 6, 8, and 10 compared with n = 1) were investigated during sequential potential cycling. Among the R(n)fluos, significant film growths were observed for the R(n)fluo with n = 1, 8, and 10. The R(8)fluo and R(10)fluo-based films were also found to consist of the monomer unit with higher molecular weight than the R(1)fluo-based film. A doping/undoping response of the new electroactive poly(R(10)fluo) film was compared with that of poly(R(8)fluo) from a fundamental viewpoint as an electrochemical capacitor material.

DOI： 10.5796/electrochemistry.75.54

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Publishing type：Research paper (scientific journal)   Publisher：Wiley-Blackwell  

DOI： 10.1002/chin.200644198

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A variety of di- and trisubstituted thiophenes were synthesized by a one-pot palladium- catalyzed ortho-alkylation sequence terminated by either Heck or C-H coupling. Initial results toward the functionalization of indoles are also presented.

DOI： 10.1021/ol061373t

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

N-Glycosylation of 2,3-dideoxy-1-[(2-pyridylmethyl)thio]glycosides (1a) using several activators is described. NBS-promoted glycosylation reaction utilizing either the alpha- or beta-thiodideoxyglycoside proceeded smoothly at -78 degrees C to give the corresponding dideoxynucleoside in a beta-selective manner, presumably through a common glycosyl donor. (c) 2006 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2006.05.060

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DOI： 10.1002/chin.200615043

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DOI： 10.1002/chin.200609212

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Electrooxidation of alcohols in water involving water-soluble N-oxyl compounds (WS-TEMPOs) proceeded smoothly to afford the corresponding ketones and aldehydes in good yields. Notably, most of WS-TEMPOs in water remained intact after the electrolysis. The aqueous solution containing WS-TEMPOs was recovered easily and repeatedly used for the electrooxidation of alcohols, offering a totally closed system. (c) 2005 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2005.10.114

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The electrooxidative glycosylation of newly designed 1-arylthio-substituted 2,3-dideoxyglycosides is described. The halide salt-mediated electrooxidation utilizing either of the alpha- or beta-thiodideoxyglycosides proceeded smoothly at -78 degrees C to give dideoxynucleosides in beta-selective manner, presumably through a 1-halo-substituted glycosyl donor.

DOI： 10.1021/ol0521776d

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Language：English   Publisher：AMER CHEMICAL SOC  

Some circumstantial evidence for the directing effect of the 2-pyridylsilyl group in the Ru-catalyzed intermolecular Pauson-Khand-type reaction (PKR) of alkenyl(2-pyridyl)silane, alkyne, and carbon monoxide has been provided. Most importantly, we have succeeded in isolating several monometallic Ru complexes relevant to the catalytic reaction: Ru(vinylsilane)(CO)(3) complexes and ruthenacyclopentene. While the stoichimetric reaction of the Ru(vinylsilane)(CO)(3) complex with an alkyne led to the formation of the corresponding cyclopentenone (PKR product) at 100 degreesC, the ruthenacyclopentene intermediate was quantitatively produced at 50 degreesC. This complex was also converted to a cyclopentenone upon heating at 100 degreesC. Moreover, it was also found that the Ru(vinylsilane)(CO)(3) complex and ruthenacyclopentene serve as catalysts in intermolecular PKR.

DOI： 10.1021/ja047484+

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Publishing type：Research paper (scientific journal)   Publisher：Wiley-Blackwell  

DOI： 10.1002/chin.200302068

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

Summarized herein are the demonstrations that the use of 2-PyMe2Si group as a removable directing group is a powerful strategy for enhancing the efficiency of otherwise sluggish processes and for steering the course of the reaction by taking advantage of attractive substrate-catalyst interaction in the palladium-catalyzed cross-coupling chemistry. The 2-PyMe2Si group-driven Heck-type coupling, Hiyama-type coupling, Stille-type coupling, and allylic alkylation are described. (C) 2002 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0022-328X(02)01173-7

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane is described. The hydrosilylation of alkenes using dimethyl(2-pyridyl)silane (2-PyMe2SiH) proceeded well in the presence of a catalytic amount of RhCI(PPh3)(3) with virtually complete regioselectivity. By taking advantage of the phase tag property of the 2-PyMe2Si group, hydrosilylation products were isolated in greater than 95% purity by simple acid-base extraction. Strategic catalyst recovery was also demonstrated. The hydrosilylation of alkynes using 2-PyMe2SiH proceeded with a Pt(CH2= CHSiMe2)(2)O/P(t-Bu)(3) catalyst to give alkenyldimethyl (2-pyridyl)silanes in good yield with high regioselectivity. A reactivity comparison of 2-PyMe2SiH with other related hydrosilanes (3-PyMe2SiH, 4-PyMe2SiH, and PhMe2SiH) was also performed. In the rhodium-catalyzed reaction, the reactivity order of hydrosilane was 2-PyMe2SiH much greater than 3-PYMe2SiH, 4-PyMe2SiH, PhMe2SiH, indicating a huge rate acceleration with 2-PyMe2SiH. In the platinum-catalyzed reaction, the reactivity order of hydrosilane was PhMe2SiH, 3-PyMe2SiH - 4-PyMe2SiH &gt; 2-PyMe2SiH, indicating a rate deceleration with 2-PyMe2SiH and 4-PyMe2SiH. It seems that these reactivity differences stem primarily from the governance of two different mechanisms (Chalk-Harrod and modified Chalk-Harrod mechanisms). From the observed reactivity order, coordination and electronic effects of dimethyl(pyridyl)silanes have been implicated.

DOI： 10.1021/jo0163389

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/1521-3773(20020916)41:18<3481::AID-ANIE3481>3.0.CO;2-X

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

The Rh- and Pt-catalyzed hydrosilylations of olefin utilizing 2-pyridyl-, 3-pyridyl-, 4-pyridyl-, and phenyldimethylsilane are described. Whereas huge rate acceleration was observed with 2-PyMe2SiH in the Ph-catalyzed reaction, huge rate deceleration was observed with 2-PyMe2SiH and 4-PyMe2SiH in the Pt-catalyzed reaction.

DOI： 10.1246/cl.2001.1088

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A novel strategy for the diversity-oriented synthesis of multisubstituted olefins, where 2-pyridyldimethyl(vinyl)silane functions as a versatile platform for olefin synthesis, is described. The palladium-catalyzed Heck-type coupling of 2-pyridyldimethyl(vinyl)silanes with organic iodides took place in the presence of Pd-2(dba)(3)/tri-2-furylphosphine catalyst to give beta -substituted vinylsilanes in excellent yields. The Heck-type coupling occurred even with alpha- and beta -substituted 2-pyridyldimethyl(vinyl)silanes. The one-pot double Heck coupling of 2-pyridyldimethyl(vinyl)silane took place with two different aryl iodides to afford beta,beta -diarylated vinylsilanes in good yields. The palladium-catalyzed Hiyama-type coupling of 2-pyridyidimethyl(vinyl)silane with organic halides took place in the presence of tetrabutylammonium fluoride to give di- and trisubstituted olefins in high yields. The sequential integration of Heck-type (or double Heck) coupling and Hiyama-type coupling produced the multisubstituted olefins in regioselective, stereoselective, and diversity-oriented fashions. Especially, the one-pot sequential Heck/Hiyama coupling reaction provides an extremely facile entry into a diverse range of stereodefined multisubstituted olefins. Mechanistic considerations of both Heck-type and Hiyama-type coupling reactions are also described.

DOI： 10.1021/ja016790+

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Wiley-Blackwell  

Facile addition of primary alkyl Gridnard reagents to vinylsilanes has been realized for the first time by exploiting the directing effect of a 2-pridyl group on silicon [Eq. (1)]. Three-component coupling reactions of a Grignard reagent, the vinylsilane, and an electrophile, followed by oxidative removal of the 2-pyridyldimethylsilyl group with H2O2 furnishes various secondary alcohols in excellent overall yields.

DOI： 10.1002/1521-3773(20010618)40:12<2337::AID-ANIE2337>3.0.CO;2-Q

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Publishing type：Research paper (scientific journal)   Publisher：Wiley-Blackwell  

DOI： 10.1002/1521-3757(20010618)113:12<2399::aid-ange2399>3.0.co;2-2

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A novel methodology for the deprotonation of a methyl group on silicon has been developed. This newly developed cr-lithiation protocol is based on the intramolecular pyridyl group coordination to stabilize the a-silyl carbanion together with the inherent silicon a effect. It was found that the deprotonation (t-BuLi/Et(2)O/-78 degreesC) occurs with 2-pyridyltrimethylsilane but not with other related silanes such as phenyltrimethylsilane, 3-pyridyltrimethylsilane, and 4-pyridyltrimethylsilane. It seems that this deprotonation proceeded through the agency of the complex-induced proximity effect (CIPE) of a 2-pyridyl group on silicon. (1)H NMR analysis of (2-pyridyldimethylsilyl)methyllithium revealed the intramolecular coordination of a pyridyl group to lithium. ( 2-Pyridyldimethylsilyl)-methyllithium was found to react with chlorosilanes, hydrosilanes, chlorostannanes, bromine, iodine, organic bromides, aldehydes, and ketones in good to excellent yields. The resultant adducts were further oxidized with H(2)O(2)/KF to give the corresponding alcohols in excellent yields. Thus, this two-step transformation provides an efficient method for the nucleophilic hydroxymethylation.

DOI： 10.1021/jo015528g

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

DOI： 10.1021/ja002582q

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

DOI： 10.1021/jo990740u

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The diastereomeric (amino)fluorosilane 2 is prepared from the prochiral (1-naphthyl)phenyldifluorosilane 5 with optically active bis[(R)-1-phenylethyl]amine (3). The two isomers of 2 can be easily separated due to their large solubility difference in CH3NO2. In addition, 2 undergoes epimerization at the silicon atom in the presence of a catalytic amount of AgF. Stereospecific methylation and the deamination-fluorination of 2 give the enantiomerically pure (1-naphthyl)phenylmethylfluorosilane (1).

DOI： 10.1021/om9904394

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

(2-Pyridyldimethylsilyl)methyl lithium was found to react with organic bromides, aldehydes, ketones, and hydrosilanes in good to excellent yields. The resultant adducts were further oxidized with H2O2/KF to give the corresponding alcohols in excellent yields. Thus, this two-step transformation provides an efficient method for hydroxymethylation. (C) 1999 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(99)01028-X

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

Novel methodology for the generation of alpha-silyl carbanion by the deprotonation of trimethylsilyl group with tert-butyllithium or LDA has been developed. This newly developed alpha-lithiation protocol is based on the intramolecular pyridyl group coordination to stabilize the alpha-silyl carbanion, together with the inherent silicon alpha effect. The importance of the use of the 2-pyridyl group in &apos;pyridyl&apos;- and &apos;silyl&apos;-directed alpha-lithiation has been confirmed by the control experiments utilizing phenyltrimethylsilane and (3-pyridyl)trimethylsilane. (C) 1999 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(99)01027-8

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Other Link： http://orcid.org/0000-0002-6744-7136

Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

(2-Pyridyldimethylsilyl)methyl lithium was found to react with organic bromides, aldehydes, ketones, and hydrosilanes in good to excellent yields. The resultant adducts were further oxidized with H2O2/KF to give the corresponding alcohols in excellent yields. Thus, this two-step transformation provides an efficient method for hydroxymethylation. (C) 1999 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(99)01028-X

DOI： 10.1016/s0040-4039(99)01028-x

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

2-Pyridyldimethylsilyl (2-PyMe2Si) group was found to serve as effective "phase: tag" for acid-base extraction for solution phase synthesis. Acid-base extraction of octyl(2-pyridyl)dimethylsilane gave rise to 98% recovery. The introduction of 2-PyMe2Si group to organic molecules was easily accomplished by Rh catalyzed hydrosilylation of alkenes with 2-PyMe2SiH. The removal of 2-PyMe2Si group was achieved by the oxidation with H2O2/KF (Tamao oxidation). In order to demonstrate the utilitiy Of 2-PyMe2Si group as a "phase tag", a sequential multi-step transformation was conducted. The products of each steps were easily isolated by acid-base extraction, and were sufficiently pure for the direct use in the next step of the sequence. (C) 1999 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4039(99)00474-8

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Other Link： http://orcid.org/0000-0002-6744-7136

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Application no：特願2005-063765  Date applied：2005.3.8

Announcement no：特開2006-249454  Date announced：2006.9.21

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Application no：特願2005-037589  Date applied：2005.2.15

Announcement no：特開2006-223345  Date announced：2006.8.31

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Application no：特願2018-193702 

Announcement no：特開2020-059687  Date announced：2020.4.16

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Country：Japan

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Country：Japan

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