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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.