Development of Reactions by Cooperative Transition-Metal Catalysis Based on Controlling Transition State of Transmetallations

2020 Fiscal Year Final Research Report

• Project/Area Number: 17KT0098
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 特設分野
• Research Field: Transition State Control
• Research Institution: Kyoto University
• Principal Investigator: Semba Kazuhiko 京都大学, 工学研究科, 助教 (30712046)
• Project Period (FY): 2017-07-18 – 2021-03-31
• Keywords: トランスメタル化 / 協働触媒 / クロスカップリング

Outline of Final Research Achievements

In this research project, studies focused on development of reactions by controlling a transition state of transmetallation between transition-metal complexes were conducted. A transition state of the stereoinvertive transmetallation between arylpalladium(II) and 1-phenylethylcopper(I) was calculated by the DFT method. The origin of the stereospecificity of the transmetallation was revealed. In addition, new transmetallations between alkylcobalt(I) and arylpalladium(II), and palladium(II) enolate and allylpalladium(II) have been found. Allylarylation of electron-deficient alkenes by cooperative Pd/Pd catalysis was developed based on the transmetallation.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

本研究で得られた立体反転を伴うトランスメタル化に関する知見は，アルキル金属反応剤の立体反転を伴うクロスカップリングの開発に重要であり，医農薬品の効率的な探索に繋がる研究成果である。また，新たなトランスメタル化に関する成果は，遷移金属協働触媒反応の開発に有用であり，本研究の知見を基礎に新たな触媒反応の開発が期待でき，我々の生活を豊かにする有機化合物の効率良い合成に繋がると期待される。実際に，本知見を基礎にパラジウム協働触媒による電子不足アルケンのアリルアリール化という反応を見出すことができた。