Precise Organic Synthesis by Developing Novel Radical Control Methods

2023 Fiscal Year Final Research Report

• Project/Area Number: 22K19016
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 33:Organic chemistry and related fields
• Research Institution: Hokkaido University
• Principal Investigator: Shimizu Yohei 北海道大学, 理学研究院, 准教授 (60609816)
• Project Period (FY): 2022-06-30 – 2024-03-31
• Keywords: ラジカル / 光 / ラジカル

Outline of Final Research Achievements

Phosphine catalysts are found to be effective in controlling the reactivity of chlorine radicals, which are known as highly reactive chemical species. The influence of the structure of the phosphine catalyst is critical, and some insights into structural features that contribute to precise control of the radical were obtained. In addition, we developed an aminochlorination of alkenes under visible light irradiation by utilizing N-chloro(fluorenone imine). This reaction starts with the addition of chlorine radicals to an alkene, and exhibits unique regio-selectivity, introducing a chlorine atom at the terminal position and an amino group at the internal position.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

これまで有効な制御方法のなかった塩素ラジカルの反応性制御にホスフィン触媒という新たな方向性を提唱するものであり、学術的意義は大きい。本方法をさらに発展させることで、一般に不活性な結合であるC(sp3)-H結合を狙った位置選択的な変換反応開発が加速され、医薬分子をはじめとした機能性分子の合成法革新に寄与すると考えられる。またアミノクロロ化反応で得られる生成物は、さまざまな変換を行うことが出来る化合物であり、機能性分子合成に資する多能性中間体として価値が高い。