TY - JOUR
T1 - Metallaphotoredox Perfluoroalkylation of Organobromides
AU - Zhao, Xiangbo
AU - MacMillan, David W.C.
N1 - Funding Information:
Financial support was provided by the National Institute of General Medical Sciences (NIGMS), the NIH (under Award R35GM134897-01), the Princeton Catalysis Initiative, and kind gifts from Merck, Janssen, BMS, Genentech, Celgene and Pfizer. X.B. is grateful for a postdoctoral fellowship from the Shanghai Institute of Organic Chemistry. We thank Yufan Liang, Ian Perry, Xiaheng Zhang, Wei Liu, and Vlad Bacauanu for their help in preparing this paper.
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/11/18
Y1 - 2020/11/18
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.0c09977
DO - 10.1021/jacs.0c09977
M3 - Article
C2 - 33164534
AN - SCOPUS:85096358553
VL - 142
SP - 19480
EP - 19486
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 46
ER -