Kochi, Takuya

写真a

Affiliation

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

Position

Associate Professor

External Links

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

Academic Degrees 【 Display / hide

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

 

Research Areas 【 Display / hide

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

Research Keywords 【 Display / hide

  • Homogeneous Catalysis

  • Synthetic Organic Chemistry

  • Organometallic Chemistry

  • Transition Metal Complexes

  • Polymer Synthesis

 

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

Papers 【 Display / hide

  • Palladium-Catalyzed Remote Diborylative Cyclization of Dienes with Diborons via Chain Walking

    Kanno S., Kakiuchi F., Kochi T.

    Journal of the American Chemical Society (Journal of the American Chemical Society)  143 ( 46 ) 19275 - 19281 2021.11

    ISSN  00027863

     View Summary

    A novel method for catalytic remote bismetalation of alkene substrates by the addition of dimetal reagents is accomplished by using chain walking. In the presence of a palladium catalyst, the reaction of various 1,n-dienes and diborons were converted into cyclopentane derivatives with two boryl groups at remote positions via facile regioselective transformation of an unactivated sp3 C-H bond to a C-B bond. Sequential construction of three distant bonds, which is difficult to achieve by any method, was accomplished for the reactions of 1,n-dienes (n ≥ 7).

  • Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β-Acetoxy Elimination

    Muto K., Kumagai T., Kakiuchi F., Kochi T.

    Angewandte Chemie - International Edition (Angewandte Chemie - International Edition)  60 ( 46 ) 24500 - 24504 2021.11

    ISSN  14337851

     View Summary

    Palladium-catalyzed remote arylative substitution was achieved for the reaction of arylboronic acids with alkenes possessing a distant acetoxy group to provide arylation products having an alkene moiety at the remote position. The use of β-acetoxy elimination as a key step in the catalytic cycle allowed for regioselective formation of unstabilized alkenes after chain walking. This reaction was applicable to various arylboronic acids as well as alkene substrates.

  • Anti-Markovnikov Addition of Anilines to Aliphatic Terminal Alkynes Catalyzed by an 8-Quinolinolato Rhodium Complex

    Morimoto Y., Kochi T., Kakiuchi F.

    Helvetica Chimica Acta (Helvetica Chimica Acta)  104 ( 10 )  2021.10

    ISSN  0018019X

     View Summary

    Anti-Markovnikov addition of anilines to aliphatic terminal alkynes proceeded using an 8-quinolinolato rhodium/phosphine catalyst system. The use of a strong organic base, 1,1,3,3,–tetramethylguanidine, in the catalyst system enabled the formation of the aldimine products. Substrates with various functional groups including polar groups such as a phenolic hydroxy group are applicable to the hydroamination.

  • Rhodium-Catalyzed Anti-Markovnikov Hydroamination of Aliphatic and Aromatic Terminal Alkynes with Aliphatic Primary Amines

    Morimoto Y., Kochi T., Kakiuchi F.

    Journal of Organic Chemistry (Journal of Organic Chemistry)  86 ( 18 ) 13143 - 13152 2021.09

    ISSN  00223263

     View Summary

    Anti-Markovnikov hydroamination of both aliphatic and aromatic terminal alkynes with primary amines was achieved using an 8-quinolinolato rhodium catalyst to form aldimines and enamines in high yields. This catalytic system realized high functional group tolerance including hydroxy, bromo, cyano, and thioester groups.

  • Deuterium-Labeling Studies on the C-H/Olefin Coupling of Aromatic Ketones Catalyzed by Fe(PMe <inf>3</inf>) <inf>4</inf>

    Kimura N., Katta S., Kitazawa Y., Kochi T., Kakiuchi F.

    Synthesis (Germany) (Synthesis (Germany))  53 ( 18 ) 3383 - 3389 2021.09

    ISSN  00397881

     View Summary

    Deuterium-labeling experiments were performed for the Fe(PMe 3) 4-catalyzed C-H/olefin coupling using a deuterium-labeled aromatic ketone with various alkenes. While the reactions with a variety of alkenes provided the linear alkylation products formed via 1,2-insertion of alkene into an Fe-H bond, the reversible 2,1-insertion proceeded during the reaction highly depends on the choice of the alkene. No H/D scrambling resulting from 2,1-insertion/β-elimination was detected for the reactions with a vinylsilane and N -vinylcarbazole, but the reactions with styrenes are considered to involve rapid 2,1-insertion/ β-elimination processes to cause significant levels of H/D scrambling.

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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

  • 連続的遠隔位官能基導入反応を基盤とする有機合成手法の開発

    2022.04
    -
    2026.03

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

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

    2018.04
    -
    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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    我々は1,10-フェナントロリン型配位子をもつパラジウム触媒を用いたチェーンウォーキングを経る1,n-ジエン類のヒドロシリル化環化反応を開発してきた。前年度にはヒドロホウ素化環化反応の検討を主に行ってきたが、この反応において収率の更なる向上が困難であったため、同時に用いる官能基化試薬についての検討を行った。その結果、当初予定していなかった反応試剤を用いた際に遠隔位への反応活性点の導入に伴う環化反応が進行することが分かった。また、反応基質の検討を行ったところ、アルキル基をもつ1,6-ジエン類を用いた際に遠隔位連続的結合形成反応が実現できることが分かった。本反応は、通常の環化異性化反応等の機構と同様の五員環形成過程の後、チェーンウォーキングにより金属を遠隔位に移動させてからσ結合メタセシスを進行させることで実現できていると考えている。一方、本反応の場合には、以前に我々が開発した反応とは異なり、環化過程より前にチェーンウォーキング機構を組み込むことが比較的困難であり、1,7-ジエンを用いた場合には五員環生成物の収率の低下が見られ、また、よりリンカー部位のメチレン鎖を長くすると更に収率が低下する結果となった。配位子としては、ヒドロシリル化環化の際に高収率を与えていた3,4,7,8-テトラメチル-1,10-フェナントロリンよりも無置換の1,10-フェナントロリンの方が収率よく目的物を与えることが分かった。溶媒としては、今まで用いていた1,2-ジクロロエタン、ジクロロメタンなどの含ハロゲン系溶媒よりも、シクロヘキサン等の低極性溶媒を用いた際に収率が向上した。
    当初予定していたヒドロボランを用いた反応における収率向上が困難であることがわかり、その後の検討で有用であることが分かった異なる反応試剤を用いて検討を行ってきたため。
    本検討で見出した反応試剤を用いた反応について詳しく検討することで、高度に官能基化された生成物の選択的合成法の開発を行う。

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

    2018.04
    -
    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
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    2019.03

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

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    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

    2022

  • SEMINAR IN CHEMISTRY

    2022

  • PRACTICAL ORGANIC CHEMISTRY

    2022

  • LABORATORIES IN SCIENCE AND TECHNOLOGY

    2022

  • LABORATORIES IN CHEMISTRY 2

    2022

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