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Efficient Access to Multifunctional Trifluoromethyl Alcohols through Base‐Free Catalytic Asymmetric C−C Bond Formation with Terminal Ynamides
Author(s) -
Cook Andrea M.,
Wolf Christian
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201510910
Subject(s) - trifluoromethyl , chemistry , ketene , catalysis , regioselectivity , stereoselectivity , yield (engineering) , amide , enantioselective synthesis , base (topology) , medicinal chemistry , combinatorial chemistry , organic chemistry , mathematics , materials science , mathematical analysis , alkyl , metallurgy
The asymmetric addition of terminal ynamides to trifluoromethyl ketones with a readily available chiral zinc catalyst gives CF 3 ‐substituted tertiary propargylic alcohols in up to 99 % yield and 96 % ee . The exclusion of organozinc additives and base as well as the general synthetic utility of the products are key features of this reaction. The value of the β‐hydroxy‐β‐trifluoromethyl ynamides is exemplified by selective transformations to chiral Z ‐ and E ‐enamides, an amide, and N,O‐ketene acetals. The highly regioselective hydration, stereoselective reduction, and hydroacyloxylation reactions proceed with high yields and without erosion of the ee value of the parent β‐hydroxy ynamides.