Asymmetric α,γ-Regioselective [3 + 3] Formal Cycloadditions of α,β-Unsaturated Aldehydes via Cascade Dienamine-Dienamine Catalysis.

Asymmetric α,γ-regioselective [3 + 3] formal cycloadditions of α,β-unsaturated aldehydes and 2-nitroallylic acetates have been developed for the first time. These reactions proceeded through a domino Michael addition-Michael addition sequence via an unusual cascade dienamine-dienamine catalysis of a chiral secondary amine, and multifunctional cyclohexene derivatives were generally constructed in moderate yields with excellent stereoselectivity after simple treatment with K2CO3.