近日,
Ruppert-Prakash试剂(TMSCF3、TMSC2F5和TMSC3F7)是一类现成的、空气中稳定的、容易操作的全氟烷基化试剂。在这项研究中,课题组人员报道了一个发生在这类氟代烷基亲核试剂和溴代芳烃/烷烃之间的、由铜催化的温和的交叉偶联反应,通过这一反应可以合成一系列不同的三氟甲基化/五氟乙基化/七氟丙基化取代物。
进一步研究表明,这个光催化的反应是通过硅烷自由基介导的卤原子提取机理实现的,因此该反应可使一系列不同位阻和电子供需的有机溴化物发生全氟烷基化。这一方法的实用性通过对几个药物类似物的高级功能化得到了展示。
附:英文原文
Title: Metallaphotoredox Perfluoroalkylation of Organobromides
Author: Xiangbo Zhao, David W. C. MacMillan
Issue&Volume: November 9, 2020
Abstract: Ruppert–Prakash type reagents (TMSCF3, TMSC2F5, and TMSC3F7) 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.
DOI: 10.1021/jacs.0c09977
Source: https://pubs.acs.org/doi/10.1021/jacs.0c09977
JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:14.612
官方网址:https://pubs.acs.org/journal/jacsat
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