We herein designed and synthesized allenyl benzoxazinones of a novel type, which were then involved in a Pd-catalyzed asymmetric cascade intramolecular cyclization/intermolecular Michael addition reaction with 1-azadienes. A broad range of chiral C2-functionalized quinoline derivatives were afforded in moderate to good yields (up to 93%) with high enantioselectivities (up to 93% ee) in this reaction.

A metal-free DBU catalyzed [3+2] cycloaddition of 3-homoacyl coumarins with cyclic 1-azadienes has been developed for the synthesis of cyclopentane-fused coumarins with excellent diastereoselectivity and complete chemoselectivity.

In the presence of organocatalyst DBU, novel spiro[benzofuranone‐cyclopentane] compounds are prepared via a [3+2] cycloaddition of benzoaurones with 3‐homoacyl coumarins. This method proceeds smoothly under mild conditions and shows tolerance for various substituent groups, affording the desired products in good yields with excellent diastereoselectivities.