Phosphine-Catalyzed (3 + 2) Annulation of γ-Substituted Cinnamic Aldehyde-Derived Morita-Baylis-Hillman Carbonates through Remote Activation.

A series of γ-substituted Morita-Baylis-Hillman (MBH) carbonates were synthesized and subjected to phosphine-catalyzed annulations with electrophilic exocyclic alkenes, giving various valuable spirocyclopentenes in moderate to excellent yields with moderate to excellent diastereoselectivities. A large scope of MBH carbonates bearing γ-hydrogen, alkenyl, and alkynyl substituents was well tolerated. The annulation unprecedentedly involves β-, γ-, and δ-carbons of MBH carbonates.