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Racemic Vinylallenes in Catalytic Enantioselective Multicomponent Processes: Rapid Generation of Complexity through 1,6-Conjugate Additions.


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 ?,?,?,?-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 B2 (pin)2 and an ?,?,?,?-unsaturated diester. A variety of vinylallenes were converted to products bearing a Z-trisubstituted alkenyl-B(pin) moiety, a vinyl group, a ?,?-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.

SUBMITTER: Huang Y 

PROVIDER: S-EPMC6481603 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Racemic Vinylallenes in Catalytic Enantioselective Multicomponent Processes: Rapid Generation of Complexity through 1,6-Conjugate Additions.

Huang Youming Y   Torker Sebastian S   Li Xinghan X   Del Pozo Juan J   Hoveyda Amir H AH  

Angewandte Chemie (International ed. in English) 20190206 9


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<sub>2</sub> (pin)<sub>2</sub> and an α,β,γ,δ-unsaturated diester. A variety of vinylallenes were converted to products bearing a Z  ...[more]

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