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 alpha'-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 beta, gamma-regioselectivity, and multifunctional products with high molecular complexity are efficiently constructed in excellent diastereo-and enantioselectivity (> 19: 1 d.r., up to 99% ee).