Chlorine Atom Transfer of Unactivated Alkyl Chlorides Enabled by Zirconocene and Photoredox Catalysis

作     者：Toshimasa Okita Kazuhiro Aida Keisuke Tanaka Eisuke Ota Junichiro Yamaguchi 

作者机构：Department of Applied ChemistryWaseda UniversityShinjukuTokyo 162-0041Japan 

出 版 物：《Precision Chemistry》 (精准化学（英文）)

年 卷 期：2023年第1卷第2期

页      面：112-118页

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：Japan Society for the Promotion of Science, JSPS, (JP21H05213, JP20K15290, 22KJ2955) Exploratory Research for Advanced Technology, ERATO, (21-IMS-C223, JPMJER1901) 

主　　题：Zirconocene Alkyl chloride Halogen atom transfer Borylation Photoredox catalysis 

摘      要：Alkyl chlorides are robust precursors to carbon radicals;however,their relative inertness has hampered their practical *** modern photochemical strategies have greatly enhanced the utility of alkyl chlorides as radical precursors,these methods often depend on strongly reducing conditions leading to unproductive side ***,we report a catalytic radical generation from 1°,2°,and 3°unactivated alkyl chlorides with zirconocene and photoredox catalysis,which enables both hydrogenation and borylation on a range of structurally complex *** mild zirconocene-catalyzed protocol shows that zirconium can render the C−Cl bond cleavage more exergonic and can lower the activation energy of the transition state,amplifying the ability of metallocenes toward halogen atom transfer.