Practical Asymmetric Alkylation of Aldehydes by Using Grignard Reagents

• Project/Area Number: 20550095
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kyoto Institute of Technology
• Principal Investigator: HARADA Toshiro Kyoto Institute of Technology, 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): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2010: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2009: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2008: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 合成化学 / 触媒・化学プロセス / 有機化学 / 有機金属化合物 / マグネシウム / 不斉合成

Research Abstract

A practical catalytic method has been developed for the enantioselective synthesis of optically active secondary alcohols by using Grignard reagents in the reaction of aldehydes. A mixed titanium reagents derived from Grignard reagents and a titanium alkoxide undergo smooth addition to various aldehydes in the presence of a chiral titanium catalyst (2mol%) to give the corresponding optically active alcohols in high yields and in high enantioselectivities.

Research Products

• [Journal Article] Catalytic Enantioselective Synthesis of Secondary Allylic Alcohols from Terminal Alkynes and Aldehydes via 1-Alkenylboron Reagents (2010)
  • Author(s): Takashi Shono, Toshiro Harada
  • Journal Title: Organic Letters 12 Pages: 5270-5273
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Synthesis of Diarylmethanols from Aryl Bromides and Aldehydes by Using Organolithium Reagents (2010)
  • Author(s): Yuya Nakagawa, Yusuke Muramatsu, Toshiro Harada
  • Journal Title: European Journal of Organic Chemistry Pages: 6535-6538
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Alkylation and Arylation of Aldehydes by Using Grignard Reagents (2010)
  • Author(s): Yusuke Muramatsu, Shinichi Kanehira, Masato Tanigawa, Yuta Miyawaki, Toshiro Harada
  • Journal Title: Bulletin of the Chemical Society of Japan 83 Pages: 19-32
  • NAID: 10027171096
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Synthesis of Diarylmethanols from Ary1 Bromides and Aldehydes by Using Organolithium Reagents (2010)
  • Author(s): 中川侑哉
  • Journal Title: Eur.J.Org.Chem. Pages: 6535-6538
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Synthesis of Secondary Allylic Alcohols from Terminal Alkynes and Aldehydes via 1-Alkenylboron Reagents (2010)
  • Author(s): 庄野隆
  • Journal Title: Org.Lett. Volume: 12 Pages: 5270-5273
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Alkylation and Arylation of Aldehydes by Using Grignard Reagents (2010)
  • Author(s): 村松雄介
  • Journal Title: Bull.Chem.Soc.Jpn. 83 Pages: 19-32
  • Peer Reviewed
• [Journal Article] Oxazaborolidinone-Catalyzed Enantioselective Friedel-Crafts Alkylation of Furans and Indoles with α,β-Unsaturated Ketones (2009)
  • Author(s): 足立慎弥
  • Journal Title: Org.Lett. 11 Pages: 5206-5209
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Aldol Additions to Ketones (2009)
  • Author(s): 足立慎弥
  • Journal Title: Eur.J.Org.Chem. 2009 Pages: 3661-3671
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Aryl Transfer Reactions to Aldehydes with Grignard Reagents as Aryl Source (2008)
  • Author(s): Yusuke Muramatsu, Toshiro Harada
  • Journal Title: Chemistry, A European Journal 14 Pages: 10560-10563
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Alkylation of Aldehydes by Using Trialkylboranes (2008)
  • Author(s): Takahiro Ukon, Toshiro Harada
  • Journal Title: European Journal of Organic Chemistry Pages: 4405-4407
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Aryl Transfer Reactions to Aldehydes with Grignard Reagents as Aryl Source (2008)
  • Author(s): 村松雄介
  • Journal Title: Chem. Eur. J. 14 Pages: 10560-10563
  • Peer Reviewed
• [Journal Article] Asymmetric Mukaiyama Aldol Reaction of Nonactivated Ketones Catalyzed by allo-Threonine-Derived Oxazaborolidinone (2008)
  • Author(s): 足立慎弥
  • Journal Title: Org. Lett. 10 Pages: 4999-5001
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Alkylation of Aldehydes by Using Trialkylboranes (2008)
  • Author(s): 右近敬浩
  • Journal Title: Eur. J. Org. Chem. 2008 Pages: 4405-4407
  • Peer Reviewed
• [Presentation] ハロゲン化有機亜鉛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 (2011)
  • Author(s): 木下雄一郎、原田俊郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜)
  • Year and Date: 2011-03-28
• [Presentation] 臭化アリールより調製した官能基化Grignard反応剤を川いるアルデヒドの触媒的不斉アリール化反応 (2011)
  • Author(s): 板倉人輔、原田俊郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜)
  • Year and Date: 2011-03-28
• [Presentation] アルデヒドへのヘテロアリールチタン反応剤の触媒的不斉付加反応 (2011)
  • Author(s): 中川侑哉、原田俊郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜)
  • Year and Date: 2011-03-28
• [Presentation] アルデヒドへのアリールチタン反応剤の触媒的不斉付加反応 (2011)
  • Author(s): 上西亜実、中川侑哉、原田俊郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜)
  • Year and Date: 2011-03-28
• [Presentation] 臭化アリールより調製した官能基化Grignard反応剤を用いるアルデヒドの触媒的不斉アリール化反応 (2011)
  • Author(s): 板倉大輔
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学(横浜)
  • Year and Date: 2011-03-28
• [Presentation] 有機リチウム反応剤を用いるアルデヒドの触媒的不斉アリール化反応 (2010)
  • Author(s): 中川侑哉、原田俊郎
  • Organizer: 第57回有機金属討論会
  • Place of Presentation: 中央大学(東京)
  • Year and Date: 2010-09-16
• [Presentation] アルケニルホウ素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 (2010)
  • Author(s): 庄野隆、原田俊郎
  • Organizer: 第57回有機金属討論会
  • Place of Presentation: 中央大学(東京)
  • Year and Date: 2010-09-16
• [Presentation] アルケニルホウ素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 (2010)
  • Author(s): 庄野隆、原田俊郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(東大阪)
  • Year and Date: 2010-03-26
• [Presentation] 有機リチウム反応剤を用いるアルデヒドの触媒的不斉アリール化反応 (2010)
  • Author(s): 中川侑哉、原田俊郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学(東大阪)
  • Year and Date: 2010-03-26
• [Presentation] 有機リチウム反応剤を用いるアルデヒドの触媒的不斉アリール化反応 (2010)
  • Author(s): 中川侑哉
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学 (東大阪)
  • Year and Date: 2010-03-26
• [Presentation] アルケニルホウ素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 (2010)
  • Author(s): 庄野隆
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学 (東大阪)
  • Year and Date: 2010-03-26
• [Presentation] Catalytic Enantioselective Alkylation and Arylation of Aldehydes by Using Grignard Reagents (2009)
  • Author(s): 原田俊郎
  • Organizer: 第11回国際有機化学京都会議(IKCOC-11)
  • Place of Presentation: リーガロイヤルホテル(京都)
  • Year and Date: 2009-11-13
• [Presentation] Catalytic Enantioselective Alkylation and Arylation of Aldehydes by Using Grignard Reagents (2009)
  • Author(s): 原田俊郎
  • Organizer: 第11回国際有機化学京都会議 (IKCOC-11)
  • Place of Presentation: リーガロイヤルホテル (京都)
  • Year and Date: 2009-11-13
• [Presentation] Catalytic Asymmetric Arylation of Aldehydes by Using Functionalized Aryl Grignard Reagents (2009)
  • Author(s): 兼平真一、村松雄介、原田俊郎
  • Organizer: 第56回有機金属討論会
  • Place of Presentation: 同志社大学(京都)
  • Year and Date: 2009-09-11
• [Presentation] Highly Efficient Catalytic Asymmetric Aryl Transfer Reactions to Aldehydes with Grignard Reagents as Aryl Source (2009)
  • Author(s): 原田俊郎、村松雄介
  • Organizer: 5-th International Symposium on Integrated Synthesis 2008 (ISIS 2008)
  • Place of Presentation: ホテル舞子ビラ(神戸)
  • Year and Date: 2009-09-05
• [Presentation] テトライソプロポキシチタン共存下でのアルデヒドへのGrignard反応剤の触媒的不斉付加反応:反応活性チタン種の検討 (2009)
  • Author(s): 村松雄介、原田俊郎
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 日本大学(船橋)
  • Year and Date: 2009-03-28
• [Presentation] 官能基を有するGrignard反応剤を用いたアルデヒドの触媒的不斉アリール化反応 (2009)
  • Author(s): 兼平真一、村松雄介、原田俊郎
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 日本大学(船橋)
  • Year and Date: 2009-03-28
• [Presentation] キラルチタン触媒によるトリアルキルボランを用いたアルデヒドの不斉アルキル化反応 (2009)
  • Author(s): 昌山一善、右近敬浩、原田俊郎
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 日本大学(船橋)
  • Year and Date: 2009-03-28
• [Presentation] テトライソプロポキシチタン共存下でのアルデヒドへのGrig-nard反応剤の触媒的不斉付加反応 : 反応活性チタン種の検討 (2009)
  • Author(s): 原田俊郎
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-28
• [Presentation] 官能基を有するGrignard反応剤を用いたアルデヒドの触媒的不斉アリール化反応 (2009)
  • Author(s): 原田俊郎
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-28
• [Presentation] キラルチタン触媒によるトリアルキルボランを用いたアルデヒドの不斉アルキル化反応 (2009)
  • Author(s): 原田俊郎
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-28
• [Presentation] Catalytic Asymmetric Arylation of Aldehydes by Using Grignard Reagents (2008)
  • Author(s): 原田俊郎、村松雄介
  • Organizer: 第55回有機金属討論会
  • Place of Presentation: 大阪府立人学(人阪)
  • Year and Date: 2008-09-30
• [Presentation] Catalytic Asymmetric Arylation of Aldehydes by Using Grignard Reagents (2008)
  • Author(s): 原田俊郎
  • Organizer: 第55回有機金属討論会
  • Place of Presentation: 大阪
  • Year and Date: 2008-09-30
• [Presentation] Catalytic Asymmetric Arylation of Aldehydes by Using Functionalized Aryl Grignard Reagents (2008)
  • Author(s): 兼平真一
  • Organizer: 第56回有機金属討論会
  • Place of Presentation: 同志社大学 (京都)
  • Year and Date: 2008-09-11
• [Presentation] Highly Efficient Catalytic Asymmetric Aryl Transfer Reactions to Aldehydes with Grignard Reagents as Aryl Source (2008)
  • Author(s): 原田俊郎
  • Organizer: 5-th International Symposium on Integrated Synthesis 2008 (ISIS 2008)
  • Place of Presentation: 神戸
  • Year and Date: 2008-09-05