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ラセミ体ハロゲン化アルキルを基質としたエナンチオ収束型不斉ホウ素置換反応の開発

Research Project

Project/Area Number 14J02341
Research Category

Grant-in-Aid for JSPS Fellows

Allocation TypeSingle-year Grants
Section国内
Research Field Organic chemistry
Research InstitutionHokkaido University

Principal Investigator

久保田 浩司  北海道大学, 大学院工学研究院, 特別研究員(PD)

Project Period (FY) 2014-04-25 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥3,070,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥270,000)
Fiscal Year 2016: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2015: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2014: ¥1,000,000 (Direct Cost: ¥1,000,000)
Keywordsホウ素 / 銅触媒 / 不斉反応 / ホウ素化 / 不斉合成
Outline of Annual Research Achievements

■ ヘテロ芳香族化合物の脱芳香族化/不斉ホウ素化 ■ < Kubota, K.; Watanabe, Y.; Hayama, K.; Ito, H. J. Am. Chem. Soc. 2016, 138, 4338.> <Kubota, K.; Watanabe, Y.; Ito, H. Adv. Synth. Catal. 2016, 358, 2379.> 入手容易なピリジンを原料とする不斉反応は、多くの医薬品の中核をなす光学活性ピペリジンを与える有用な手法である。本研究では、ピリジンの部分還元により得られる1,2-ジヒドロピリジンに対し、不斉銅(I)触媒存在下、ジボロンを作用させると光学活性ボリルピペリジンが高立体選択的に得られることを見出した。また同様の触媒系はキノリンにも適用可能であり、別報として報告した。
■ 脂肪族および芳香族アルデヒド類の求核的不斉ホウ素化反応の機構解明 ■ < Kubota, K.; Jin, M.; Ito, H. Organometallics 2016, 35, 136.> 我々は以前、銅(I)触媒を用いたアルデヒド類のエナンチオ選択的ホウ素化反応を報告した。本研究では、理論計算により、位置選択性やエナンチオ選択性発現機構をはじめとする反応の詳細を明らかにし、今後の反応設計における重要な知見が得られた。
■ キラルアニオン相間移動触媒による不斉プメラー反応の開発 ■ < Kubota, K.; Biswas. S; Turberg, M. Dean F. Toste, Manuscript under preparation> チオニウムカチオンへの付加反応を経由するプメラー型変換反応は、含硫黄化合物を合成する上で有用な手法である。本研究では、キラルアニオン相関移動触媒を用いることで酸化的不斉プメラー反応の開発に初めて成功した。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Report

(3 results)
  • 2016 Annual Research Report
  • 2015 Annual Research Report
  • 2014 Annual Research Report
  • Research Products

    (24 results)

All 2017 2016 2015 2014

All Journal Article (11 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 11 results,  Acknowledgement Compliant: 9 results) Presentation (13 results) (of which Int'l Joint Research: 3 results,  Invited: 1 results)

  • [Journal Article] Formal nucleophilic borylation and borylative cyclization of organic halides2017

    • Author(s)
      Koji Kubota, Hiroaki Iwamoto, Hajime Ito
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 15 Issue: 2 Pages: 285-300

    • DOI

      10.1039/c6ob02369j

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Enantioselective Synthesis of Chiral Piperidines via the Stepwise Dearomatization/Borylation of Pyridines2016

    • Author(s)
      Kubota, K.; Watanabe, Y.; Hayama, K.; Ito, H.
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 13 Issue: 13 Pages: 4338-4341

    • DOI

      10.1021/jacs.6b01375

    • Related Report
      2016 Annual Research Report 2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of Enantiomerically Enriched Chiral Tetrahydroquinolines via Sequential Dearomatization/Enantioselective Borylation Reactions2016

    • Author(s)
      Kubota, K.; Watanabe, Y.; Ito, H.
    • Journal Title

      Adv. Synth. Catal.

      Volume: 15 Issue: 15 Pages: 2379-2384

    • DOI

      10.1002/adsc.201600372

    • NAID

      120006331853

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Computational Insight into the Enantioselective Nucleophilic Borylation of a Polarized C=O Double Bond Catalyzed by Di-phosphine-Borylcopper(I) Complexes2016

    • Author(s)
      Kubota, K.; Jin, M.; Ito, H.
    • Journal Title

      Organometallics

      Volume: 35 Issue: 10 Pages: 1376-1383

    • DOI

      10.1021/acs.organomet.5b00621

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Highly Selective Markovnikov Hydroboration of Alkyl-Substituted Terminal Alkenes with a Phosphine-Copper(I) Catalyst2016

    • Author(s)
      Iwamoto, H.; Kubota, K.; Ito, H.
    • Journal Title

      Chem. Commun.

      Volume: 印刷中 Issue: 35 Pages: 5916-5919

    • DOI

      10.1039/c6cc00782a

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper(I)-Catalyzed Diastereoselective Borylative Exo-Cyclization of Alkenyl Aryl Ketones2015

    • Author(s)
      Copper(I)-Catalyzed Diastereoselective Borylative Exo-Cyclization of Alkenyl Aryl Ketones
    • Journal Title

      Synlett

      Volume: 26 Issue: 02 Pages: 272-276

    • DOI

      10.1055/s-0035-1560721

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Enantioselective Borylative Dearomatization of Indoles through Copper(I) Catalysis2015

    • Author(s)
      Kubota, K.; Hayama, K.; Iwamoto, H.; Ito, H.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 54 Issue: 30 Pages: 8809-8813

    • DOI

      10.1002/anie.201502964

    • NAID

      120005763139

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reaction Optimization, Scalability, and Mechanistic Insight in the Catalytic Enantioselective Desymmetriyation of 1,1-Diborylalkanes via Suzuki-Miyaura Cross-Coupling2015

    • Author(s)
      Sun, H.; Kubota, K.; Hall, D. G.
    • Journal Title

      Chemistry - A European Journal

      Volume: 21 Issue: 52 Pages: 19186-19194

    • DOI

      10.1002/chem.201406680

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Copper(I)-Catalyzed Carbon-Halogen Bond-Selective Boryl Substitution of Alkyl Halides Bearing Terminal Alkene Moieties2015

    • Author(s)
      Iwamoto, H.; Kubota, K.; Yamamoto, E.; Ito, H.
    • Journal Title

      Chemical Communication

      Volume: 51 Issue: 47 Pages: 9655-9658

    • DOI

      10.1039/c5cc02760h

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Copper(I)-Catalyzed Enantioselective Nucleophilic Borylation of Aldehydes: An Efficient Route to Enantiomerically Enriched α-Alkoxyorganoboronate Esters2015

    • Author(s)
      Kubota, K.; Yamamoto, E.; Ito, H.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 137 Issue: 1 Pages: 420-424

    • DOI

      10.1021/ja511247z

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Silicon-Tethered Strategy for Copper(I)-Catalyzed Stereo- and Regioselective Alkylboration of Alkynes2015

    • Author(s)
      Kubota, K.; Iwamoto, H.; Yamamoto, E; Ito, H.
    • Journal Title

      Organic Letters

      Volume: 17 Issue: 3 Pages: 620-623

    • DOI

      10.1021/ol503620n

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Enantioselective Nucleophilic Borylation of Carbonyl Compounds2016

    • Author(s)
      Koji Kubota
    • Organizer
      Reaxys PhD Prize
    • Place of Presentation
      London
    • Year and Date
      2016-09-22
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 銅(I)触媒による1,2-ジヒドロピリジン類の位置およびエナンチオ選択的ホウ素化反応2016

    • Author(s)
      久保田浩司、渡邉裕太、羽山慶一、伊藤肇
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学 (京都府京都市)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] Copper(I)-Catalyzed Enantioselective Borylative Dearomatiztion of Indoles2016

    • Author(s)
      Koji Kubota, Keiichi Hayama, Hiroaki Iwamoto, Hajime Ito
    • Organizer
      フロンティア化学教育研究センター (FCC) 第4回国際シンポジウム
    • Place of Presentation
      北海道大学 (北海道札幌市)
    • Year and Date
      2016-02-23
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Dearomatization of Indoles by Copper Catalysis2015

    • Author(s)
      Koji Kubota, Keiichi Hayama, Hiroaki Iwamoto, Hajime Ito
    • Organizer
      The International Chemical Congress of Pacific Basin Societies 2015 (Pacifichem)
    • Place of Presentation
      ハワイ (アメリカ)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 銅(I)触媒によるホウ素化反応の新展開2015

    • Author(s)
      久保田浩司
    • Organizer
      若手研究者のための有機化学札幌セミナー
    • Place of Presentation
      北海道大学 (北海道札幌市)
    • Year and Date
      2015-11-26
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] Selective Synthesis of Organoborons by Copper(I) Catalysis2015

    • Author(s)
      Koji Kubota
    • Organizer
      第6回大津会議
    • Place of Presentation
      大津プリンスホテル (滋賀県大津市)
    • Year and Date
      2015-10-17
    • Related Report
      2015 Annual Research Report
  • [Presentation] Enantioselective Nucleophilic Borylation of Carbonyl Compounds Using Copper(I) Catalysis2015

    • Author(s)
      Koji Kubota, Eiji Yamamoto, Hajime Ito
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学 (大阪府吹田市)
    • Year and Date
      2015-09-07
    • Related Report
      2015 Annual Research Report
  • [Presentation] ボリル銅(I)活性種を用いた求核的ホウ素化反応の開発2015

    • Author(s)
      久保田浩司
    • Organizer
      第48回有機金属若手の会夏の学校
    • Place of Presentation
      白浜荘(滋賀県高島市)
    • Year and Date
      2015-07-13
    • Related Report
      2015 Annual Research Report
  • [Presentation] Copper(I)-Catalyzed Enantioselective Nucleophilic Borylation of Aldehydes2015

    • Author(s)
      ○Koji Kubota, Eiji Yamamoto, Hajime Ito
    • Organizer
      日本化学会 第95春季年会
    • Place of Presentation
      日本大学 (東京都千代田区)
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] Asymmetric Nucleophilic Borylation of Aldehydes Catalyzed by a Chiral Phosphine-Copper(I) Complex2014

    • Author(s)
      ○Koji Kubota, Eiji Yamamoto, Hajime Ito
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九州大学 (福岡県福岡市)
    • Year and Date
      2014-09-23 – 2014-09-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] Enantioselective Monoborylation of Aldehydes Catalyzed by a Chiral Phosphine-Copper(I) Complex2014

    • Author(s)
      ○Koji Kubota, Eiji Yamamoto, Hajime Ito
    • Organizer
      XXVI International Conference on Organometallic Chemistry (ICOMC 2014)
    • Place of Presentation
      ロイトンホテル札幌 (北海道札幌市)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] Copper(I)-Catalyzed Asymmetric Monoborylation of C-O Double Bond2014

    • Author(s)
      ○Koji Kubota, Eiji Yamamoto, Hajime Ito
    • Organizer
      ISHC-XIX
    • Place of Presentation
      オタワ (カナダ)
    • Year and Date
      2014-07-06 – 2014-07-11
    • Related Report
      2014 Annual Research Report
  • [Presentation] Copper(I)-Catalyzed Asymmetric borylation of Aldehydes2014

    • Author(s)
      ○Koji Kubota, Eiji Yamamoto, Hajime Ito
    • Organizer
      フロンティア化学教育研究センター(FCC)第3回国際シンポジウム
    • Place of Presentation
      北海道大学 (北海道札幌市)
    • Year and Date
      2014-06-16 – 2014-06-17
    • Related Report
      2014 Annual Research Report

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Published: 2015-01-22   Modified: 2024-03-26  

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