In:
Angewandte Chemie International Edition, Wiley, Vol. 58, No. 9 ( 2019-02-25), p. 2685-2691
Abstract:
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.
Type of Medium:
Online Resource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.201812535
Language:
English
Publisher:
Wiley
Publication Date:
2019
detail.hit.zdb_id:
2011836-3
detail.hit.zdb_id:
123227-7
