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Enantioselective Conjugate Silyl Additions to α,β‐Unsaturated Aldehydes Catalyzed by Combination of Transition Metal and Chiral Amine Catalysts
Author(s) -
Ibrahem Ismail,
Santoro Stefano,
Himo Fahmi,
Córdova Armando
Publication year - 2011
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201000908
Subject(s) - chemistry , enantioselective synthesis , stereocenter , silylation , catalysis , nucleophile , aldehyde , iminium , amine gas treating , conjugate , organic chemistry , transition metal , organocatalysis , addition reaction , transition state , combinatorial chemistry , mathematical analysis , mathematics
We report that transition metal‐catalyzed nucleophilic activation can be combined with chiral amine‐catalyzed iminium activation as exemplified by the unprecedented enantioselective conjugate addition of a dimethylsilanyl group to α,β‐unsaturated aldehydes. These reactions proceed with excellent 1,4‐selectivity to afford the corresponding β‐silyl aldehyde products 3 in high yields and up to 97:3 er using inexpensive bench stable copper salts and simple chiral amine catalysts. The reaction can also generate a quaternary stereocenter with good enantioselectivity. Density functional calculations are performed to elucidate the reaction mechanism and the origin of enantioselectivity.