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Enantioselective CH Bond Functionalization Triggered by Radical Trifluoromethylation of Unactivated Alkene
Author(s) -
Yu Peng,
Lin JinShun,
Li Lei,
Zheng ShengCai,
Xiong YaPing,
Zhao LiJiao,
Tan Bin,
Liu XinYuan
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201405401
Subject(s) - enantioselective synthesis , trifluoromethylation , alkene , chemistry , reagent , brønsted–lowry acid–base theory , catalysis , hydride , combinatorial chemistry , surface modification , stereoselectivity , medicinal chemistry , organic chemistry , trifluoromethyl , alkyl , hydrogen
An asymmetric unactivated alkene/CH bond difunctionalization reaction for the concomitant construction of CCF 3 and CO bonds was realized by using a Cu/Brønsted acid cooperative catalytic system, thus providing facile access to valuable chiral CF 3 ‐containing N,O‐aminals with excellent regio‐, chemo‐, and enantioselectivity. Mechanistic studies revealed that this reaction may proceed by an unprecedented 1,5‐hydride shift involving activation of unactivated alkenes and a radical trifluoromethylation to initiate subsequent enantioselective functionalization of CH bonds. Control experiments also suggested that chiral Brønsted acid plays multiple roles and not only controls the stereoselectivity but also increases the reaction rate through activation of Togni’s reagent.