有机溴化物的金属光氧化还原全氟烷基化反应
Metallaphotoredox Perfluoroalkylation of Organobromides.
作者信息
Zhao Xiangbo, MacMillan David W C
机构信息
Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
出版信息
J Am Chem Soc. 2020 Nov 18;142(46):19480-19486. doi: 10.1021/jacs.0c09977. Epub 2020 Nov 9.
Abstract
Ruppert-Prakash type reagents (TMSCF, TMSCF, and TMSCF) are readily available, air-stable, and easy-to-handle fluoroalkyl sources. Herein, we describe a mild, copper-catalyzed cross-coupling of these fluoroalkyl nucleophiles with aryl and alkyl bromides to produce a diverse array of trifluoromethyl, pentafluoroethyl, and heptafluoropropyl adducts. This light-mediated transformation proceeds via a silyl-radical-mediated halogen atom abstraction pathway, which enables perfluoroalkylation of a broad range of organobromides of variable steric and electronic demand. The utility of the method is demonstrated through the late-stage functionalization of several drug analogues.
摘要
鲁珀特 - 普拉卡什型试剂（TMSCF、TMSCF和TMSCF）是易于获得、对空气稳定且易于处理的氟代烷基源。在此，我们描述了一种温和的、铜催化的这些氟代烷基亲核试剂与芳基和烷基溴的交叉偶联反应，以生成各种三氟甲基、五氟乙基和七氟丙基加合物。这种光介导的转化通过硅基自由基介导的卤原子夺取途径进行，这使得能够对具有不同空间和电子需求的多种有机溴化物进行全氟烷基化。该方法的实用性通过几种药物类似物的后期官能团化得到了证明。
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