Development of Novel Chiral Multifunctional Ligands and Application to Asymmetric Catalysis

• Project/Area Number: 19750026
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: YOSHIKAI Naohiko The University of Tokyo, 大学院・理学系研究科, 助教 (50401170)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥3,580,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥480,000); Fiscal Year 2008: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2007: ¥1,500,000 (Direct Cost: ¥1,500,000)
• Keywords: 不斉合成 / 有機金属化学 / 配位子 / 計算化学

Research Abstract

遷移金属原子と典型金属原子に同時に配位しうる,新しい光学活性多座配位子の合成と,不斉触媒反応への応用を行った.アミノ酸から容易に誘導されるアミノヒドロキシホスフィン配位子が,銅触媒と有機亜鉛試薬を用いたアリル位置換反応において極めて高い位置および立体選択性を与えることを見出した.また,本触媒系を含めて,有機銅反応剤によるアリル位置換反応において位置および立体選択性が発現する要因を理論的に明らかにした.

Research Products

• [Journal Article] Enantioselective Copper-Catalyzed Allylic Substitution Reaction with Aminohydroxyphosphine Ligand (2009)
  • Author(s): N. Yoshikai, K. Miura, E. Nakamura
  • Journal Title: Adv. Synth. Catal. (in press)
• [Journal Article] Enantioselective Copper-Catalyzed Allylic Substitution Reaction with Aminohydroxyphosphine Ligand (2009)
  • Author(s): N. Yoshikai, K. Miura, E. Nakamure
  • Journal Title: Advanced Synthesis & Catalysis 351(印刷中)(掲載確定)
  • Peer Reviewed
• [Journal Article] Origin of the Regio- and Stereoselectivity of Allylic Substitution of Organocopper Reagents (2008)
  • Author(s): N. Yoshikai, S.-L. Zhang, E. Nakamura
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 12862-12863
• [Journal Article] Origin of the Regio- and Stereoselectivity of Allylic Substitution of Organocopper Reagents (2008)
  • Author(s): N. Yoshikai, S.-L. Zhang, E. Nakamura
  • Journal Title: Journal of the American Chemical Society 130 Pages: 12862-12863
  • Peer Reviewed
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Pennsylvania
  • Place of Presentation: Philadelphia, USA
  • Year and Date: 2008-12-15
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Pennsylvania
  • Place of Presentation: フィラデルフィア
  • Year and Date: 2008-12-15
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Chicago
  • Place of Presentation: Chicago, USA
  • Year and Date: 2008-12-12
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Chicago
  • Place of Presentation: シカゴ
  • Year and Date: 2008-12-12
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Michigan
  • Place of Presentation: Ann Arbor, USA
  • Year and Date: 2008-12-11
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Michigan
  • Place of Presentation: アナーバー
  • Year and Date: 2008-12-11
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Massachusetts Institute of Technology
  • Place of Presentation: Boston, USA
  • Year and Date: 2008-12-09
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Massachusetts Institute of Technology
  • Place of Presentation: ボストン
  • Year and Date: 2008-12-09
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Boston College
  • Place of Presentation: Boston, USA
  • Year and Date: 2008-12-08
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Boston College
  • Place of Presentation: ボストン
  • Year and Date: 2008-12-08
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Columbia University
  • Place of Presentation: New York, USA
  • Year and Date: 2008-12-05
• [Presentation] ctivation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallic (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Columbia University
  • Place of Presentation: ニユーヨーク
  • Year and Date: 2008-12-05
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Nanyang Technological University
  • Place of Presentation: Singapore
  • Year and Date: 2008-09-09
• [Presentation] Activation of Unreactive Carbon-Halogen and Carbon-Hydrogen Bonds by Transition Metal Catalysis of Nucleophilic Organometallics (2008)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at Nanyang Technological University
  • Place of Presentation: シンガポール
  • Year and Date: 2008-09-09
• [Presentation] Bimetallic Synergism in Copper Catalysis : From Theoretical Study to Reaction Design (2008)
  • Author(s): N. Yoshikai
  • Organizer: International Symposium on Molecular Theory for Real Systems
  • Place of Presentation: 京都
  • Year and Date: 2008-07-28
• [Presentation] Design of Copper and Nickel Catalysis Based on Cooperative Effect of Transition Metal and Lewis Acid (2007)
  • Author(s): N. Yoshikai
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2007
  • Place of Presentation: Singapore
  • Year and Date: 2007-12-18
• [Presentation] Design of Copper and Nickel Catalysis Based on Cooperative Effect of Transitio nMetal and Lewis Acid (2007)
  • Author(s): N. Yoshikai
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2007
  • Place of Presentation: シンガポール
  • Year and Date: 2007-12-18
• [Presentation] 遷移金属-典型金属協働作用に基づく炭素-炭素結合生成反応の開発 (2007)
  • Author(s): 吉戒直彦, 松田広和, Alakananda Hajra, 中村栄一
  • Organizer: 日本化学会第1回関東支部大会
  • Place of Presentation: 東京
  • Year and Date: 2007-09-27
• [Presentation] Bimetallic Synergism in Copper Catalysis (2007)
  • Author(s): N. Yoshikai
  • Organizer: Theoretical Study to Reaction Design, International Symposium on Molecular Theory for Real Systems
  • Place of Presentation: Kyoto, Japan
  • Year and Date: 2007-07-28
• [Presentation] Synergy of Transition Metal and Lewis Acid in Copper and Nickel Catalysis (2007)
  • Author(s): N. Yoshikai
  • Organizer: Mechanistic Study to Reaction Design, Seminar at University of Wisconsin-Madison
  • Place of Presentation: Madison, USA
  • Year and Date: 2007-07-23
• [Presentation] Synergy of Transition Metal and Lewis Acid in Copper and Nickel Catalysis : From Mechanistic Study to Reaction Design (2007)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Wisconsin-Madison
  • Place of Presentation: マディソン
  • Year and Date: 2007-07-23
• [Presentation] Synergy of Transition Metal and Lewis Acid in Copper and Nickel Catalysis (2007)
  • Author(s): N. Yoshikai
  • Organizer: Mechanistic Study to Reaction Design, Seminar at University of Montreal
  • Place of Presentation: Montreal, Canada
  • Year and Date: 2007-07-13
• [Presentation] Synergy of Transition Metal and Lweis Acid in Copper and Nickel Catalysis : From Mechanistic Study to Reaction Design (2007)
  • Author(s): N. Yoshikai
  • Organizer: Seminar at University of Montreal
  • Place of Presentation: モントリオール
  • Year and Date: 2007-07-13
• [Book] "Theory of Organocopper-mediated Reactions" in Chemistry of Organocopper Compounds (Eds.: Z. Rapopport and I. Marek) (2009)
  • Author(s): E. Nakamura, N. Yoshikai
  • Publisher: Wiley(in print)
• [Book] Chemistry of Organocopper Compounds(分担執筆) (2009)
  • Author(s): E. Nakamura, N. Yoshikai
  • Publisher: John Wiley & Sons(印刷中)(掲載確定)
• [Book] Chemistry of Organocopper Compounds (分担執筆) (2009)
  • Author(s): E. Nakamura, N. Yoshikai
  • Publisher: John Wiley & Sons(印刷中)(掲載確定)