Vicinal stereocenters asymmetric allylic alkylation and Cope rearrangement: a straightforward route to functionally and stereochemically rich heterocycles.

An asymmetric allylic alkylation/Cope rearrangement (AAA/[3,3]) capable of stereoselectively constructing vicinal stereocenters has been developed. Strategically integrated 4-methylation on the 3,3-dicyano-1,5-diene controls stereoselectivity and drives Cope rearrangement equilibrium in the forward direction. The AAA/[3,3] sequence rapidly converts abundant achiral and racemic starting materials into valuable (hetero)cycloalkane building blocks bearing significant functional and stereochemical complexity, highlighting the value of (hetero)cyclohexylidenemalononitriles as launching points for complex heterocycle synthesis.