Cross‐conjugated Trienamine Catalysis with α′‐Alkylidene 2‐Cyclohexenones: Application in β,γ‐Regioselective Aza‐Diels–Alder Reaction

Endo ‐type cross‐conjugated trienamines between highly congested α′‐alkylidene 2‐cyclohexenones and a chiral primary amine catalyst serve as HOMO‐raised dienophiles in inverse‐electron‐demand aza‐Diels–Alder cycloadditions with a number of 1‐azadiene substrates. The reactions exhibit exclusive β,γ‐regioselectivity, and multifunctional products with high molecular complexity are efficiently constructed in excellent diastereo‐ and enantioselectivity (>19:1 d.r., up to 99 %  ee ).