Abstract The intermolecular α‐allylation of enals and enones occurs by the condensation of variously substituted allenamides with allylic alcohols. Cooperative catalysis by [Au(I t Bu)NTf 2 ] and AgNTf 2 enables the synthesis of a range of densely functionalized α‐allylated enals, enones, and acyl silanes in good yield under mild reaction conditions. DFT calculations support the role of an α‐gold(I) enal/enone as the active nucleophilic species.
