Strategy for catalytic stereocontrol of carbon radicals

2022 Fiscal Year Final Research Report

• Project/Area Number: 21K18957
• 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: Nagoya University
• Principal Investigator: Ooi Takashi 名古屋大学, 工学研究科(WPI), 教授 (80271708)
• Project Period (FY): 2021-07-09 – 2023-03-31
• Keywords: クロスカップリング / ラジカル / 分子認識 / 分子触媒

Outline of Final Research Achievements

The highly efficient atom-transfer radical addition of pinacol (bromomethyl)boronate to styrenes has been developed based on the appropriate use of thiourea, the anion-binding organic molecular catalyst, and photoredox catalyst. The catalytic, in-situ formation of the hydrobromide salt of borylated isothiourea from boronate and thiourea and subsequent single-electron reduction of the thiouronium group by excited photocatalyst lead to generate boryl methyl radical with concomitant liberation of thiourea via mesolytic cleavage of the C-S bond. This catalysis provides rapid access to synthetically versatile compounds having wo reactive functional groups, a boronate and a halogen.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究成果のように化学反応を精密に制御するための方法論を開拓し、従来困難であった反応を実現することは、最小単位のものづくりである合成化学において普遍的に重要な価値をもつ。革新的な新薬や電子機器デバイスの機能ユニットを創出する手段となるだけはなく、既存の有用な物質を、卑近な原料からより低コストで環境負荷を低減しながらつくり出すプロセスの実現にもつながる。