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Racemic Vinylallenes in Catalytic Enantioselective Multicomponent Processes: Rapid Generation of Complexity through 1,6‐Conjugate Additions
Author(s) -
Huang Youming,
Torker Sebastian,
Li Xinghan,
del Pozo Juan,
Hoveyda Amir H.
Publication year - 2019
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.201812535
Subject(s) - enantioselective synthesis , stereocenter , conjugate , moiety , olefin fiber , chemistry , catalysis , vicinal , yield (engineering) , stereochemistry , organic chemistry , materials science , mathematical analysis , mathematics , metallurgy
Racemic vinylallenes are shown to be effective substrates for catalytic multicomponent diastereo‐ and enantioselective 1,6‐conjugate addition of multifunctional allyl moieties to easily accessible α,β,γ,δ‐unsaturated diesters. Reactions may be catalyzed by 5.0 mol % of a readily accessible NHC‐Cu complex at ambient temperature, and other than a vinylallene, involve B 2 (pin) 2 and an α,β,γ,δ‐unsaturated diester. A variety of vinylallenes were converted to products bearing a Z‐trisubstituted alkenyl‐B(pin) moiety, a vinyl group, a β,γ‐unsaturated diester unit, and vicinal stereogenic centers in up to 67 % yield, 87:13 Z / E ratio, >98:2 d.r., and 98:2 e.r. Chemoselective modifications involving the alkenyl‐B(pin), the vinyl, or the 1,2‐disubstituted olefin moieties were carried out to demonstrate versatility and utility. Stereochemical models, based on mechanistic and DFT studies, demonstrate the dynamic behavior of intermediated Cu‐allyl species and account for various selectivity profiles.