Development of Strong Bronsted Base Hybrid Catalyst Systems for Stereoselective Carbon-Carbon Bond Forming Reactions

2021 Fiscal Year Final Research Report

• Project Area: Hybrid Catalysis for Enabling Molecular Synthesis on Demand
• Project/Area Number: 17H06448
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The University of Tokyo
• Principal Investigator: Yamashita Yasuhiro 東京大学, 大学院理学系研究科(理学部), 准教授 (90334341)
• Project Period (FY): 2017-06-30 – 2022-03-31
• Keywords: 強塩基 / 触媒 / 不斉合成 / ハイブリッド / 固相塩基

Outline of Final Research Achievements

We have developed a hybrid catalyst system consisting of a strong base catalyst and a metal or organo catalyst, and applied for catalytic stereoselective reactions using a raw material that is easily available but has poor reactivity. Catalytic asymmetric Mannich reactions using a propionamide, which is a weakly acidic compound, and catalytic asymmetric addition reactions of alkylarenes, such as toluene, and propylene with imines were realized by using chiral strong base hybrid catalyst systems. By constructing a hybrid catalyst system of a base catalyst and an organo photocatalyst, we developed catalytic reactions between styrenes and malonic acid esters, which do not react using the base catalyst alone. We have also developed K/γ-Al2O3 as a strong solid base catalyst and realized catalytic 1,4-addition reactions of a propionamide in a flow reaction system.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

構造が単純で入手容易な原料を用いて、医薬品等の高付加価値な有機分子を短工程で合成するための方法論の開発は、合成過程で生じる廃棄物の低減化や省エネルギー化につながるため、社会的意義の大きい環境調和型有機合成を実現する上で最も期待されている研究の一つである。本研究では、医薬品合成中間体として有用な化合物を、安価で入手容易であるが反応性に乏しい原料から直接触媒反応により立体選択的に合成することに成功した。これらの触媒反応は、従来の手法では実現が困難であり、その実現は学術的意義が大きいと言える。