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Development of Chiral Magnesium and Aluminum Catalysts for Practically Fast Enantioselective Carbonyl Addition Reaction

Research Project

Project/Area Number 15K05500
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, 分子化学系, 教授 (30135628)

Co-Investigator(Kenkyū-buntansha) 楠川 隆博  京都工芸繊維大学, 分子化学系, 准教授 (70300720)
Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2017: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2016: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2015: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords不斉触媒 / 不斉合成 / 不斉付加反応 / 合成化学
Outline of Final Research Achievements

Chiral aluminum catalyst system has been developed for the enantioselective vinylation of aldehydes. Disubstituted (E)-vinylaluminum reagents, generated regio- and stereoselectively by the carboalumination of terminal alkynes with trimethylaluminum, were used straightforwardly without transmetalation to vinyltitanium reagents in subsequent enantioselective addition to aldehydes with a 3,5-diphenylphenyl-H8-BINOL-derived chiral aluminum catalyst at low catalyst loading (5 mol%). The reaction afforded the corresponding enantiomerically enriched secondary allylic alcohols with a reversal of selectivity observed in closely relevant reactions catalyzed by a chiral titanium complex derived from the same ligand.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (12 results)

All 2018 2017 2016 2015

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Acknowledgement Compliant: 5 results) Presentation (4 results)

  • [Journal Article] Silica-Supported Catalyst for Enantioselective Arylation of Aldehydes under Batch and Continuous-Flow Conditions2018

    • Author(s)
      Watanabe Satoshi、Nakaya Naoyuki、Akai Junichiro、Kanaori Kenji、Harada Toshiro
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 9 Pages: 2737-2740

    • DOI

      10.1021/acs.orglett.8b00945

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Method for Catalytic Enantioselective Alkylation of Aldehydes Using Grignard Reagents as Alkyl Sources2018

    • Author(s)
      Tanaka Kento、Tomihama Munehisa、Yamamoto Koji、Matsubara Naoki、Harada Toshiro
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 83 Issue: 11 Pages: 6127-6132

    • DOI

      10.1021/acs.joc.8b00929

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Application of a Heterogeneous Chiral Titanium Catalyst Derived from Silica-Supported 3-Aryl H8-BINOL to Enantioselective Alkylation and Arylation of Aldehydes2017

    • Author(s)
      Akai Junichiro、Watanabe Satoshi、Michikawa Kumiko、Harada Toshiro
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 13 Pages: 3632-3635

    • DOI

      10.1021/acs.orglett.7b01625

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Practical Method for the Catalytic Enantioselective Arylation and Heteroarylation of Ketones with Organotitanium Reagents Generated in situ from Bromide and Heteroarene Precursors2017

    • Author(s)
      Atsushi Matsuda, Tomoya Ushimaru, Yusuke Kobayashi, Toshiro Harada
    • Journal Title

      Chem. Eur. J.

      Volume: 23 Issue: 36 Pages: 8605-8609

    • DOI

      10.1002/chem.201701395

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Chiral Aluminum Catalyst System for the Enantioselective Addition of Vinylaluminum Reagents to Aldehydes: Metal Controlled Reversal of Enantioselectivity2016

    • Author(s)
      Priyanka A. Adate, Takuya Matsunaga, Shin Hirata, Toshiro Harada
    • Journal Title

      Adv. Syn. Catal.

      Volume: 358 Issue: 23 Pages: 3688-3693

    • DOI

      10.1002/adsc.201600594

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Development of Highly Active Chiral Titanium Catalysts for the Enantioselective Addition of Various Organometallic Reagents to Aldehydes2016

    • Author(s)
      Toshiro Harada
    • Journal Title

      Chem. Record

      Volume: 16 Issue: 3 Pages: 1256-1273

    • DOI

      10.1002/tcr.201500269

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Enhancement of Catalytic Activity of Chiral H8-BINOL Titanium Complexes by Introduction of Sterically Demanding Group at the 3 Position2016

    • Author(s)
      Yasuki Hayashi, Nobuaki Yamamura, Takahiro Kusukawa, Toshiro Harada
    • Journal Title

      Chem. Eur. J.

      Volume: 22

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Catalytic Enantioselective Synthesis of Trisubstituted Secondary Allylic Alcohols Beginning with Terminal Alkynes and Aldehydes2015

    • Author(s)
      Hideki Morimoto, Toshiro Harada
    • Journal Title

      Eur. J. Org. Chem.

      Volume: 2015 Issue: 33 Pages: 7378-7383

    • DOI

      10.1002/ejoc.201500910

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Grignard反応剤を用いるアルデヒドの触媒的不斉アルキル化反応2017

    • Author(s)
      田中健翔、山本晃嗣、原田俊郎
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] シリカ担持3-アリール-H8-BINOLキラルチタン触媒によるアルデヒドの不斉アルキル化及びアリール化2017

    • Author(s)
      渡辺諭史、赤井淳一郎、道川功実子、原田俊郎
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 臭化物より調製したアリールチタン反応剤を直接用いる実用的なケトンの触媒的不斉アリール化及びヘテロアリール化反応2017

    • Author(s)
      松田温、小林勇介、原田俊郎
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 臭化物より調製したアリールチタン反応剤を用いるケトンの触媒的不斉アリール化反応2016

    • Author(s)
      松田温,、牛丸朋也、原田俊郎
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2019-03-29  

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