通过光氧化还原催化实现三氟甲基烯烃的无金属脱氟芳基化反应。
Metal-free defluorinative arylation of trifluoromethyl alkenes via photoredox catalysis.
作者信息
Wiles Rebecca J, Phelan James P, Molander Gary A
机构信息
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104-6323, USA.
出版信息
Chem Commun (Camb). 2019 Jul 7;55(53):7599-7602. doi: 10.1039/c9cc04265b. Epub 2019 Jun 14.
Abstract
Literature methods to access gem-difluoroalkenes are largely limited to harsh, organometallic-based methods, and known photoredox-mediated processes are not amenable to aryl radical addition to trifluoromethyl alkenes. A metal-free, functional group-tolerant method for the preparation of benzylic gem-difluoroalkenes is described. Halogen atom abstraction from (hetero)aryl halides generates aryl radicals that undergo a defluorinative arylation of α-trifluoromethyl alkenes, tolerating electronically disparate aryl radicals and α-trifluoromethyl alkenes.
摘要
获取偕二氟烯烃的文献方法在很大程度上限于苛刻的、基于有机金属的方法，并且已知的光氧化还原介导的过程不适用于芳基自由基加成到三氟甲基烯烃上。本文描述了一种用于制备苄基偕二氟烯烃的无金属、官能团耐受性方法。从（杂）芳基卤化物中夺取卤原子会产生芳基自由基，这些自由基会对α-三氟甲基烯烃进行脱氟芳基化反应，能够耐受电子性质不同的芳基自由基和α-三氟甲基烯烃。
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