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Development of Catalytic Method for Enantioselective Addition of Conventional Organometallic Reagents

Research Project

Project/Area Number 24550118
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionKyoto Institute of Technology

Principal Investigator

HARADA Toshiro  京都工芸繊維大学, 工芸科学研究科, 教授 (30135628)

Co-Investigator(Kenkyū-buntansha) KUSUKAWA Takahiro  京都工芸繊維大学, 工芸科学研究科, 准教授 (70300720)
Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2013: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2012: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywords合成化学 / 触媒 / 不斉合成 / 触媒反応 / 不斉付加 / 不斉触媒 / 不斉付加反応
Outline of Final Research Achievements

The enantioselective addition of conventional organometallic reagents, such as organolithium, organozinc halides, organoboron, and organoaluminum reagents, to aldehydes is realized by the catalysis of chiral titanium complex derived from H8-BINOL derivatives bearing a bulky aryl group at the 3-position. As these organometallic reagents can be prepared readily from commercial precursors, a variety of enantiomerically enriched secondary alcohols are now available in a one-step reaction. The reaction of organozinc halides and organoboron reagents bearing functional group provides an access to the poly-functionalized chiral secondary alcohols that are often utilized in the asymmetric synthesis of pharmaceuticals.

Report

(4 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • 2012 Research-status Report
  • Research Products

    (20 results)

All 2015 2014 2013 2012

All Journal Article (4 results) (of which Peer Reviewed: 4 results) Presentation (16 results) (of which Invited: 6 results)

  • [Journal Article] Catalytic Enantioselective Synthesis of α-Substituted Secondary Allylic Alcohols from Terminal Alkynes and Aldehydes via Vinylaluminum Reagents2013

    • Author(s)
      R. Kumar, H. Kawasaki, and T. Harada
    • Journal Title

      Chem. Eur. J.

      Volume: 19 Issue: 52 Pages: 17707-17710

    • DOI

      10.1002/chem.201303619

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Alkylation of Aldehydes Using Functionalized Alkylboron Reagents Catalyzed by a Chiral Titanium Complex2013

    • Author(s)
      R. Kumar, H. Kawasaki, and T. Harada
    • Journal Title

      Org. Lett.

      Volume: 15 Issue: 16 Pages: 4198-4201

    • DOI

      10.1021/ol4019248

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Practical Enantioselective Arylation and Heteroarylation of Aldehydes with In Situ Prepared Organotitanium Reagents Catalyzed by 3-Aryl H8-BINOL Derived Titanium Complexes2013

    • Author(s)
      A. Uenishi, Y. Nakagawa, H. Osumi, and T. Harada,
    • Journal Title

      Chemistry - A European Journal

      Volume: 19 Pages: 4896-4905

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Alkylation of Aldehydes by Using Organozinc Halide Reagents2013

    • Author(s)
      Y. Kinoshita, S. Kanehira, Y. Hayashi, and T. Harada
    • Journal Title

      Chemistry - A European Journal

      Volume: 19 Pages: 3311-3314

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Presentation] キラルアルミニウム触媒によるビニルアルミニウム反応剤のアルデヒドへの触媒的不斉付加反応2015

    • Author(s)
      松永拓也、Priyanka Adate, 原田俊郎
    • Organizer
      日本化学会第95回春季年会
    • Place of Presentation
      日本大学理工学部(千葉県・船橋市)
    • Year and Date
      2015-03-26
    • Related Report
      2014 Annual Research Report
  • [Presentation] 高活性キラルチタン触媒による実用的なアルデヒドの不斉アリール化反応2015

    • Author(s)
      山村宣晶、原田俊郎
    • Organizer
      日本化学会第95回春季年会
    • Place of Presentation
      日本大学理工学部(千葉県・船橋市)
    • Year and Date
      2015-03-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] Catalytic Enantioselective Vinylation of Aldehydes Using Lithium Reagents2014

    • Author(s)
      Taku Ohmura, Toshiro Harada
    • Organizer
      有機金属化学討論会
    • Place of Presentation
      九州大学医学部(福岡県・福岡市)
    • Year and Date
      2014-09-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] Enhanced Catalytic Activity of Chiral H8-BINOL Titanium Complexes by Introduction of Sterically Demanding Group at 3 Position2014

    • Author(s)
      Yasuki, Hayashi, Nobuaki Yamamura, Takahiro Kusukawa, Toshiro Harada
    • Organizer
      有機金属化学討論会
    • Place of Presentation
      九州大学医学部(福岡県・福岡市)
    • Year and Date
      2014-09-24
    • Related Report
      2014 Annual Research Report
  • [Presentation] Catalytic Enantioselective Alkenylation of Aldehydes Using Vinylaluminium Reagents Generated from Terminal Alkynes2014

    • Author(s)
      Ravindra Kumar, Hiroki Kawasaki, Haruki Morimoto, Toshiro Harada
    • Organizer
      The XXVI International Conference on Organometallic Chemistry
    • Place of Presentation
      北海道・札幌市
    • Year and Date
      2014-07-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] リチウム反応剤を用いるアルデヒドの触媒的不斉アルケニル化反応2014

    • Author(s)
      大村拓、原田俊郎
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] 3位へのかさ高いアリール基の導入によるキラルH8-BINOLチタン触媒の高活性化2014

    • Author(s)
      山村宣晶、原田俊郎
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] 3-アリール-H8-BINOL誘導体より調製されるキラルチタン触媒が示す高活性の要因2014

    • Author(s)
      林保輝、楠川隆博、原田俊郎
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Catalytic Enantioselective Alkenylation of Aldehydes Uising-beta-Disubstituted Vinylaluminum Reagents Generated by Zr-Catalyzed Carboalumination of Terminal Alkynes2013

    • Author(s)
      H. Morimoto, T. Harada
    • Organizer
      60th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      学習院大学
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Catalytic Enantioselective Alkenylation of Aldehydes Uising alpha-Substituted Vinylaluminum Reagents Generated by Ni-Catalyzed Hydroalumination of Terminal Alkynes2013

    • Author(s)
      H. Kawasaki, R. Kumar, T. Harada
    • Organizer
      60th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      学習院大学
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Catalytic Enantioselctive Addition of Functionalized Alkyl Groups to Aldehydes by Using Organozinc and Organoboron Reagents2013

    • Author(s)
      Y. Kinoshita, R. Kumar, H. Kawasaki, S. Kanehira, Y. Hayashi, T. Harada
    • Organizer
      10th International Symposium on Carbanion Chemistry
    • Place of Presentation
      京都
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] ハロゲン化アルキル亜鉛反応剤を用いるα,β-不飽和アルデヒドの触媒的不斉アルキル化反応2013

    • Author(s)
      林 保輝、原田 俊郎
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学草津キャンパス
    • Related Report
      2012 Research-status Report
  • [Presentation] 3-アリール-H8-BINOL誘導体より調製される高活性キラルチタン触媒の構造2013

    • Author(s)
      上西 亜実、原田 俊郎
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学草津キャンパス
    • Related Report
      2012 Research-status Report
  • [Presentation] ブロモアルケン及びアルデヒドを原料に用いる第二級アリルアルコールの触媒的不斉合成2013

    • Author(s)
      大村 拓、原田 俊郎
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学草津キャンパス
    • Related Report
      2012 Research-status Report
  • [Presentation] 末端アルキンのニッケル触媒ヒドロアルミ化により調製したα-アルケニルアルミニウム反応剤を用いるアルデヒドの触媒的不斉アルケニル化反応2013

    • Author(s)
      Ravindra Kumar、原田 俊郎
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学草津キャンパス
    • Related Report
      2012 Research-status Report
  • [Presentation] Enantioselective Alkylation of Aldehydes Using Functionalized Alkylboron Reagents Catalyzed by a Chiral Titanium Complex2012

    • Author(s)
      Ravindra Kumar, Hiroki Kawasaki, and Toshiro Harada
    • Organizer
      第59回有機金属化学討論会
    • Place of Presentation
      大阪大学吹田キャンパス
    • Related Report
      2012 Research-status Report

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Published: 2013-05-31   Modified: 2019-07-29  

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