Cooperative Organocatalysis for the Asymmetric γ Alkylation of α‐Branched Enals

α Branched leads to γ : The direct and enantioselective γ alkylation of α‐substituted α,β‐unsaturated aldehydes under dienamine catalysis has been achieved. A cooperative catalysis system that involves dienamine activation of α‐branched enals and chiral Brønsted acid catalysis promotes an S N 1‐alkylation pathway while ensuring complete γ‐site selectivity and high stereocontrol (see scheme; Bn=benzyl).