Kochi, Takuya

写真a

Affiliation

Faculty of Science and Technology, Department of Chemistry （Yagami）

Position

Associate Professor

External Links
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Career 【 Display / hide 】

  • 2004.10
    -
    2006.03

    東京大学大学院工学系研究科　産学官連携研究員

  • 2006.04
    -
    2007.03

    日本学術振興会　特別研究員PD

  • 2007.04
    -
    2010.03

    慶應義塾大学理工学部化学科　助教

  • 2010.04
    -
    2017.03

    慶應義塾大学理工学部化学科　専任講師

  • 2017.04
    -
    Present

    慶應義塾大学理工学部化学科　准教授

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Academic Background 【 Display / hide 】

  • 1998.03

    The University of Tokyo, Faculty of Engineering, Department of Chemistry and Biotechnology

    University, Graduated

  • 2000.03

    The University of Tokyo, Graduate School of Engineering, Department of Chemistry and Biotechnology

    Graduate School, Completed, Master's course

  • 2004.09

    University of California, Berkeley, Department of Chemistry

    United States, Graduate School, Completed, Doctoral course

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Academic Degrees 【 Display / hide 】

  • Ph.D., University of California, Berkeley, Coursework, 2004.12

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Research Areas 【 Display / hide 】

  • Nanotechnology/Materials / Synthetic organic chemistry (Synthetic Chemistry)

  • Nanotechnology/Materials / Synthetic organic chemistry (Synthetic Chemistry)

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Research Keywords 【 Display / hide 】

  • Homogeneous Catalysis

  • Homogeneous Catalysis

  • Synthetic Organic Chemistry

  • Synthetic Organic Chemistry

  • Organometallic Chemistry

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Books 【 Display / hide 】

  • 有機電解合成の新潮流

    河内卓彌、垣内史敏, シーエムシー出版, 2021.11

    Scope: 電解C–H官能基化,  Contact page： 57-70

  • ハートウィグ有機遷移金属化学（翻訳）

    小宮三四郎, 穐田宗隆, 岩澤伸治, 穐田宗隆, 石井洋一, 伊藤肇, 岩澤伸治, 上野圭司, 大江浩一, 河内 卓彌, 小宮三四郎, 近藤輝幸, 中尾佳亮, 西原康師, 水田勉, 東京化学同人, 2015.03

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Papers 【 Display / hide 】

  • Palladium-Catalyzed Electrochemical Iodination of 1-Arylpyridine N-Oxides

    Zhou H., Miyasaka M., Wang Y.H., Kochi T., Kakiuchi F.

    Journal of Organic Chemistry （Journal of Organic Chemistry)   2023

    ISSN  00223263

    　View Summary

    The palladium-catalyzed C-H iodination of 1-arylpyridine N-oxides proceeded under electrochemical oxidation conditions using I2 as an iodine source. The reaction of isoquinoline N-oxides possessing various para- or meta-substituted aryl groups at the 1-position proceeded to give the corresponding iodination products. Electron-donating groups on the aryl group facilitated the reaction to give relatively high yields of the product. The reaction was also found to be applicable to 2-aryl-3-picoline N-oxides.

  • Conformational Isomerization as a Process to Determine Selectivity over Reaction Pathways: Effect of Alkene Rotation in Chain Walking via Cis Alkene Intermediates

    Muto K., Hatanaka M., Kakiuchi F., Kochi T.

    Journal of Organic Chemistry （Journal of Organic Chemistry)  89 （ 7 ） 4712 - 4721 2024.04

    ISSN  00223263

    　View Summary

    In organic reactions, bond-forming and bond-cleaving processes are generally considered to be more important than other processes such as conformational isomerization. We report herein an example where a conformational isomerization process, propeller-like alkene rotation, is considered to determine the selectivity over the reaction pathways. The transition state with the highest energy barrier in some alkylpalladium isomerization (chain walking) events was theoretically indicated to correspond to alkene rotation, while transition states for bond-cleaving β-hydride elimination and bond-forming migratory insertion were not even observed. It was also suggested both theoretically and experimentally that the palladium chain walking over internal carbons in alkyl chains proceeds via cis alkene intermediates rather than thermodynamically more stable trans alkene intermediates, due to their relative difficulty to undergo alkene rotation.

  • Off/on Switching of Electric Current as a Strategy for One-Pot Synthesis of Bromoarylpyridines by Cross-Coupling/ C−H Bromination

    Hirota Y., Fujie T., Kochi T., Kakiuchi F.

    Israel Journal of Chemistry （Israel Journal of Chemistry)  64 （ 1-2 ）  2024.01

    ISSN  00212148

    　View Summary

    An “OFF/ON” electric current switching protocol was developed as a new strategy for one-pot organic synthesis. Suzuki-Miyaura coupling of 2-bromopyridines with arylboronic acids in an electrochemical cell was performed without applying an electric current, and subsequently, the Pd-catalyzed electrochemical C−H bromination was conducted using the already-present Pd catalyst to obtain 2-(2-bromoaryl)pyridines as products. The one-pot synthesis of bromoarenes can also be achieved without adding an external Br source in the second step. Furthermore, an OFF/ON/OFF two-times switching protocol also realized the formation of an N-containing teraryl derivative.

  • Rhodium-Catalyzed β-Acylalkylation of Allylbenzene Derivatives with Allyl Alcohols via C-C Bond Cleavage

    Ishikawa S., Togashi R., Ueda R., Onodera S., Kochi T., Kakiuchi F.

    Journal of Organic Chemistry （Journal of Organic Chemistry)  88 （ 5 ） 3313 - 3320 2023.03

    ISSN  00223263

    　View Summary

    We report here a deallylative β-acylalkylation reaction of allylbenzene derivatives with allyl alcohols in the presence of Cp*Rh catalysts. Allylbenzenes possessing pyridyl and pyrazolyl directing groups were converted to β-aryl ketones via the cleavage of C(aryl)-C(allyl) bonds. Synthesis of a quinoline derivative from a β-aryl ketone product bearing a pyrazolyl group was also achieved.

  • Palladium-Catalyzed Hydroboration/Cyclization of 1,n-Dienes

    Kanno S., Kakiuchi F., Kochi T.

    Journal of Organic Chemistry （Journal of Organic Chemistry)  88 （ 4 ） 2621 - 2630 2023.02

    ISSN  00223263

    　View Summary

    While the hydroboration of alkenes is well established, the corresponding cyclization reaction of dienes remains challenging. Here, we report a new method for hydroboration/cyclization applicable to various 1,n-dienes and hydroboranes. The method features the direct synthesis of borylalkyl cyclopentanes from common 1,6-dienes, which is highlighted by syntheses of elaborated pyrrolidine cores from easily accessible diallylamines. Notably, 1,n-dienes (n > 6) also undergo five-membered ring formation, offering “remote” hydroboration/cyclization that would be otherwise difficult to achieve.

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Papers, etc., Registered in KOARA 【 Display / hide 】

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Reviews, Commentaries, etc. 【 Display / hide 】

  • Palladium-Catalyzed Aromatic C−H Functionalizations Utilizing Electrochemical Oxidations

    Kakiuchi F., Kochi T.

    Chemical Record (Chemical Record)  21 ( 9 ) 2320 - 2331 2021.09

    ISSN  15278999

    　View Summary

    Transition-metal-catalyzed electrochemical C−H functionalizations have been extensively studied as atom- and step-economical clean methods in organic synthesis. In this account, we described our efforts on the palladium-catalyzed electrochemical C−H functionalizations, including C−H halogenations of arylpyridines and benzamide derivatives using HCl/HBr and I2 as a halogen source, a one-pot process giving teraryls via the palladium-catalyzed electrochemical C−H iodination and subsequent Suzuki-Miyaura coupling, and an iodine-mediated oxidative homo-coupling reaction of arylpyridines.

  • New strategy for catalytic oxidative CH functionalization: Efficient combination of transition-metal catalyst and electrochemical oxidation

    Kakiuchi F., Kochi T.

    Chemistry Letters (Chemistry Letters)  49 ( 10 ) 1256 - 1269 2020.10

    ISSN  03667022

    　View Summary

    Transition-metal-catalyzed CH functionalizations have been extensively studied as atom- and step-economical methods in organic synthesis. Oxidative CH functionalization is one of the most extensively studied reactions in this area, but it is often necessary to deactivate the remaining oxidants and to remove the wastes derived from chemical oxidants. During the past few years, a combination of transition-metal-catalyzed CH activation and electrochemical oxidation has become a commonly-used environmentally-benign strategy for catalytic oxidative CH functionalization. In this review, we briefly survey studies regarding the transition-metal-catalyzed oxidative CH functionalization with the aid of electrochemical oxidation.

  • Nondissociative chain walking as a strategy in catalytic organic synthesis

    Kochi T, Kanno S, Kakiuchi F

    Tetrahedron Letters (Tetrahedron Letters)  60 ( 37 )  2019.09

    ISSN  00404039

    　View Summary

    © 2019 Elsevier Ltd “Nondissociative” chain walking is a mechanism where an alkylmetal species undergoes rapid β-hydride elimination and reinsertion to move the metal center along the alkyl chain without dissociating an alkene intermediate during the migration process. This digest summarizes the unique characteristics of the nondissociative chain walking mechanism compared to the stepwise alkene isomerization mechanism and their use in catalytic organic synthesis.

  • Catalytic Reactions of Terminal Alkynes Using Rhodium(I) Complexes Bearing 8-Quinolinolate Ligands

    Kakiuchi F, Takano S, Kochi T

    ACS Catalysis (ACS Catalysis)  8 ( 7 ) 6127 - 6137 2018.07

    ISSN  2155-5435

    　View Summary

    © 2018 American Chemical Society. 8-Quinolinolate is a monoanionic, hard, strongly σ-donating ligand that can form strong chelates with various metals. However, studies of the catalytic activities of soft transition metal complexes such as greater than second row, low-valent, late-transition metals having 8-quinolinolate ligands had not been well explored until recently. In recent years, several research groups including our own have studied and developed various reactions of terminal alkynes using rhodium(I) catalysts containing an 8-quinolinolate ligand. In this Perspective, we surveyed the transformations of terminal alkynes using 8-quinolinolato rhodium(I) catalyst such as additions of alcohols, amines, and thiols as well as polymerization, trimerization, dimerization, and alkyne/alkene [2 + 2] cycloaddition. Mechanistic studies based on theoretical calculations of hydroalkoxylation of alkynes and alkyne/alkene [2 + 2] cycloaddition reactions have also been described.

  • Selective C-H Functionalizations by Electrochemical Reactions with Palladium Catalysts

    Fumitoshi Kakiuchi, and Takuya Kochi

    Isr. J. Chem. 57 ( 10-11 ) 953 - 963 2017.11

    Joint Work

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Research Projects of Competitive Funds, etc. 【 Display / hide 】

  • Development of Methods for Organic Synthesis Based on Sequential Functionalization of Remote Sites

    2022.04
    -
    2026.03

    Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (B), No Setting

    　View Summary

    本研究は、申請者が研究を推進してきたチェーンウォーキングを経る触媒的有機小分子合成を基盤として、合成化学上困難かつ最近の重要課題である遠隔位二官能基化反応(Remote Difunctionalization)、さらには従来困難であった三つ以上の遠隔位連続結合生成反応の開発を行い、実用的な触媒的有機合成手法としての深化を試みるものである。

  • Development of New Methods for Sequential Remote Bond Formation Based on the Chain Walking Mechanism

    2018.04
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    2022.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, 河内 卓彌, Grant-in-Aid for Scientific Research (B), Principal investigator

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    Various sequential formation of distant bonds was achieved by the use of functionalization reagents such as diborons and hydroboranes in the palladium-catalyzed chain-walking cyclization of 1,n-dienes. Sequential formation of "three" distant bonds, which is unprecedented and difficult to achieve otherwise, was also realized in the reactions of 1,n-dienes (n>6) with diborons. Formal sigma-bond metathesis between Pd-C and B-B bonds,a rarely considered process,is suggested to be involved in the final step of the catalytic cycles of the reaction using diborons and to proceed easily.

  • Asymmetric Functionalization of Unreactive C-H Bonds via Chain Walking Using Precisely Designed Catalysts

    2018.04
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    2020.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, 河内 卓彌, Grant-in-Aid for Scientific Research on Innovative Areas, Principal investigator

    　View Summary

    最近我々は、パラジウム触媒を用いた1,n-ジエン類のヒドロシリル化環化反応により、シリルアルキル基をもつ五員環生成物が得られることを見出している。本反応においてはチェーンウォーキングという反応点を遠隔位に選択的に移動させられる過程を組み込むことで、一つの触媒サイクルにおいて離れた位置で連続的に結合形成を行うことに成功している。そこで、本反応においても光学活性配位子を利用することで、不斉触媒反応へと展開できるのではないかと考え、三置換アルケン部位と末端アルケン部位を併せもつ1,8-ジエンについて不斉ヒドロシリル化環化反応を検討した。この基質のヒドロシリル化環化反応は光学活性でない配位子を用いた場合にも収率45%でしか目的物を得られていなかったが、含窒素光学活性二座配位子を用いた場合には収率の更なる低下が見られた。室温条件ではごく少量しか目的物は得られなかったが、反応温度を60度以上にすると収率は15％まで向上した。ヒドロシランの当量を減らすと環化せずにヒドロシリル化のみが起こった副生成物の生成は抑制できた一方、目的物の収率は同程度であった。また、ヒドロシランの当量を増やした場合には、副生成物の生成が促進され、目的物の収率の低下が見られた。さらに、溶媒量の検討を行ったが、収率の向上には至らなかった。これらの検討において、ヒドロシリル化環化生成物のエナンチオマー過剰率はほぼ73%程度で大きな変化は見られなかった。
    令和元年度が最終年度であるため、記入しない。
    令和元年度が最終年度であるため、記入しない。

  • Developments of New Molecular Transformations Using Soft Transition Metal Catalysts Bearing a Hard Ligand

    2016.04
    -
    2019.03

    Grants-in-Aid for Scientific Research, Kakiuchi Fumitoshi, Grant-in-Aid for Scientific Research (B), No Setting

    　View Summary

    In this research project, we have investigated developments of new catalytic reactions of terminal alkynes with nucleophilnes using quinolinolato-rhodium complexes as a catalyst. We synthesized a variety of rhodium complexes having a tridentate phosphine-containing quinolinolate ligand (PNO ligand). This (PNO)rhodium complexes showed a unique catalytic activity for reactions of terminal alkynes with nucleophiles such as amines. We used the (PNO)rhodium catalyst in a hydroaminative cyclization reaction of enynes with secondary amines. The reaction of 2-vinylphenylacetylenes with secondary amines gave 2-aminoindenes in good yields via hydroaminative cyclization. The reaction is considered to proceed via carbon-carbon bond formation on a catalytically generated aminocarbene ligand. To the best of our knowledge, this reaction is the first application of aminocarbene ligands catalytically generated in situ from organic substrates to carbon-carbon bond forming reactions.

  • チェーンウォーキングを活用したプロキラルなメチレンの不斉官能基化

    2016.04
    -
    2018.03

    MEXT,JSPS, Grant-in-Aid for Scientific Research, 河内 卓彌, Grant-in-Aid for Scientific Research on Innovative Areas, Principal investigator

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Awards 【 Display / hide 】

  • Incentive Award in Synthetic Organic Chemistry, Japan

    KOCHI Takuya, 2016.02, The Society of Synthetic Organic Chemistry, Japan, 革新的な物質活性化法を駆使した新しい触媒的分子変換法の開発

    Type of Award： Award from Japanese society, conference, symposium, etc.

  • Thieme Chemistry Journals Award 2015

    Takuya Kochi, 2015.01, Georg Thieme Verlag

    Type of Award： International academic award (Japan or overseas),  Country： Germany

  • Banyu Chemist Award 2014

    河内　卓彌, 2014.12, 公益財団法人　万有生命科学振興国際交流財団, 新規物質活性化法を駆使した革新的な触媒的官能基変換法の開発

    Type of Award： Award from publisher, newspaper, foundation, etc.

  • 第1回新化学技術研究奨励賞

    河内　卓彌, 2012.05, 公益社団法人　新化学技術推進協会, 元素資源代替としての電気を利用した革新的触媒プロセスの開発

    Type of Award： Award from Japanese society, conference, symposium, etc.

  • The Young Scientists’ Prize, The Commendation for Science and Technology by the Minister of Education, Culture, Sports, Science and Technology

    KOCHI Takuya, 2012.04, 遷移金属触媒を用いた革新的な極性官能基導入法の研究

    Type of Award： Other

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Courses Taught 【 Display / hide 】

  • TOPICS IN ORGANOMETALLIC CHEMISTRY 2

    2024

  • SEMINAR IN CHEMISTRY

    2024

  • PRACTICAL ORGANIC CHEMISTRY

    2024

  • LABORATORIES IN SCIENCE AND TECHNOLOGY

    2024

  • LABORATORIES IN CHEMISTRY 2

    2024

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