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Efficient direct asymmetric hydrogenation of N-heteroaromatic compounds to produce optically active cyclic amines

Research Project

Project/Area Number 25620083
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

MASHIMA Kazushi  大阪大学, 基礎工学研究科, 教授 (70159143)

Project Period (FY) 2013-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2013: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords不斉水素化反応 / 複素芳香環化合物 / キノリン類 / キノキサリン類 / イソキノリン類 / ジヒドリドイリジウム錯体 / イリジウム二核錯体 / 外圏六員環遷移状態 / 不斉水素化 / イソキノリン / イリジウム / テトラヒドロイソキノリン / ヒドリド錯体 / ハロゲン架橋イリジウム二核錯体 / 光学活性2座ホスフィン配位子 / 複核イリジウム錯体 / ピペリジン / ピリジン塩酸塩 / 光学活性ピペリジン誘導体 / 含窒素複素環化合物
Outline of Final Research Achievements

We found that asymmetric hydrogenation of 1- and 3-substituted and 1,3-disubstituted isoquinolinium chlorides using triply halide-bridged dinuclear iridium complexes [{Ir(H)(diphosphine)}2(μ-Cl)3]Cl (1) proceeded when we applied the strategy of the HCl salt formation of isoquinolines to afford the corresponding chiral 1,2,3,4-tetrahydroisoquinolines (THIQs) in high yield and excellent enantioselectivity after simple basic workup.
Effects of the salt formation were carefully evaluated based on controlled experiments including time-course experiments, 1H and 31P{1H} NMR studies, isolation, and characterization of several intermediates. Together with the function of the chloride anion of the isoquinolinium chlorides, we proposed a new outer-sphere mechanism including a coordination of the chloride anion of the substrates to an iridium dihydride species along with a hydrogen bond between the chloride ligand and the N-H proton of substrate salts.

Report

(3 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • Research Products

    (9 results)

All 2015 2014 2012 Other

All Journal Article (4 results) (of which Peer Reviewed: 4 results,  Acknowledgement Compliant: 1 results) Presentation (3 results) Remarks (2 results)

  • [Journal Article] Enhancing Effects of Salt Formation on Catalytic Activity and Enantioselelectivity for Asymmetric Hydrogenation of Isoquinolinium Salts by Dinuclear Halide-Bridged Iridium Complexes Bearing Chiral Diphosphine Ligands2015

    • Author(s)
      Yusuke Kita, Kenta Yamaji, Kosuke Higashida, Sathaiah Kandula, Atsuhiro Iimuro, Kazushi Mashima*
    • Journal Title

      Chemistry A European Journal

      Volume: 21 Issue: 5 Pages: 1915-1927

    • DOI

      10.1002/chem.201405408

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Iridium-catalyzed Asymmetric Hydrogenation of Pyridinium Salts for Constructing Multiple Stereogenic Centers on Piperidines2014

    • Author(s)
      Yusuke Kita, Atsuhiro Iimuro, Shoji Hida, Kazushi Mashima
    • Journal Title

      Chemistry Letter

      Volume: 43 Issue: 3 Pages: 284-286

    • DOI

      10.1246/cl.130943

    • NAID

      130004868004

    • Related Report
      2014 Annual Research Report 2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Additive Effects on Asymmetric Hydrogenation of N-Heteroaromatics2014

    • Author(s)
      Takuto Nagano, Atsuhiro Iimuro, Kenta Yamaji, Yusuke Kita, Kazushi Mashima
    • Journal Title

      Heterocycles

      Volume: 80 Issue: 1 Pages: 103-127

    • DOI

      10.3987/rev-13-sr(s)2

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Hydrogenation of Isoquinolinium Salts Catalyzed by Chiral Iridium Complexes : Direct Synthesis for Optically Active 1, 2, 3, 4-Tetrahydroisoquinolines2012

    • Author(s)
      Atsuhiro Iimuro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 52 Issue: 7 Pages: 2046-2050

    • DOI

      10.1002/anie.201207748

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Presentation] キラルジホスフィン配位子を有するイリジウム二核錯体を用いたキナゾリン類塩の不斉水素化反応2015

    • Author(s)
      東田 皓介、飯室 敦弘、喜多 祐介、真島 和志
    • Organizer
      日本化学会 第95春季年会
    • Place of Presentation
      日本大学 理工学部船橋キャンパス/薬学部
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] イリジウム触媒によるイソキノリン類の不斉水素化反応における基質の塩形成の効果2015

    • Author(s)
      喜多 祐介、山地 健太、東田 皓介、飯室 敦弘、真島 和志
    • Organizer
      日本化学会 第95春季年会
    • Place of Presentation
      日本大学 理工学部船橋キャンパス/薬学部
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] イリジウム 2 核錯体を用いた多置換ピリジン塩類の触媒的不斉水素化反応2014

    • Author(s)
      樋田翔士、飯室敦弘、喜多祐介、真島和志
    • Organizer
      第94春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Research-status Report
  • [Remarks] 真島研究室

    • URL

      http://www.organomet.chem.es.osaka-u.ac.jp/

    • Related Report
      2014 Annual Research Report
  • [Remarks] Mashima Lab.

    • URL

      http://www.organomet.chem.es.osaka-u.ac.jp/

    • Related Report
      2013 Research-status Report

URL: 

Published: 2014-07-25   Modified: 2019-07-29  

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