Distinct reactivity of Morita-Baylis-Hillman acetates as a novel C(2) component in amine-catalyzed [2 + 2 + 2] and [2 + 4] annulations.

Amine-catalyzed [2 + 2 + 2] and [2 + 4] annulations of Morita-Baylis-Hillman (MBH) acetates with cyano activated alkenes and 1,3-azadienes have been developed to provide cyclohexanes and tetrahydropyridines. In the annulations, MBH acetates serve as a novel C(2) component with an inactive homoallylic methyl involved in the bond formation.