A radical approach to the copper oxidative addition problem

Trifluoromethylation of bromoarenes

Chip Le, Tiffany Q. Chen, Tao Liang, Patricia Zhang, David W.C. MacMillan

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.

Original languageEnglish (US)
Pages (from-to)1010-1014
Number of pages5
JournalScience
Volume360
Issue number6392
DOIs
StatePublished - Jun 1 2018

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Copper
Catalysis
Halogens
Bromides

All Science Journal Classification (ASJC) codes

  • General

Cite this

Le, Chip ; Chen, Tiffany Q. ; Liang, Tao ; Zhang, Patricia ; MacMillan, David W.C. / A radical approach to the copper oxidative addition problem : Trifluoromethylation of bromoarenes. In: Science. 2018 ; Vol. 360, No. 6392. pp. 1010-1014.
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A radical approach to the copper oxidative addition problem : Trifluoromethylation of bromoarenes. / Le, Chip; Chen, Tiffany Q.; Liang, Tao; Zhang, Patricia; MacMillan, David W.C.

In: Science, Vol. 360, No. 6392, 01.06.2018, p. 1010-1014.

Research output: Contribution to journalArticle

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AU - Chen, Tiffany Q.

AU - Liang, Tao

AU - Zhang, Patricia

AU - MacMillan, David W.C.

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