4 years ago

Achiral Pyridine Ligand-Enabled Enantioselective Radical Oxytrifluoromethylation of Alkenes with Alcohols

Achiral Pyridine Ligand-Enabled Enantioselective Radical Oxytrifluoromethylation of Alkenes with Alcohols
Xiao-Yang Dong, Yong-Feng Cheng, Zhang-Long Yu, Qiang-Shuai Gu, Xin-Yuan Liu
A conceptually novel strategy with achiral pyridine as the ancillary ligand to stabilize high-valent copper species for the first asymmetric radical oxytrifluoromethylation of alkenes with alcohols under CuI/phosphoric acid dual-catalysis has been developed. The transformation features mild reaction conditions, a remarkably broad substrate scope and excellent functional group tolerance, offering an efficient approach to a wide range of trifluoromethyl-substituted tetrahydrofurans bearing an α-tertiary stereocenter with excellent enantioselectivity. Mechanistic studies support the presumed role of the achiral pyridine as a coordinative ligand on copper metal to stabilize the key transient reaction species involved in the asymmetric induction process. Magic pyridine: Achiral pyridine has been shown to be crucial for accomplishing the first asymmetric radical oxytrifluoromethylation of unactivated alkenes with alcohols. The remarkably enhanced enantioselectivity observed has been accounted for by a stabilizing effect of pyridine on high-valent copper intermediates as an ancillary ligand.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702925

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