A cooperative Pd/Co catalysis system for the asymmetric (4+2) cycloaddition of vinyl benzoxazinones with N-acylpyrazoles

Abstract

Transition metal-catalyzed cycloaddition has been established as a powerful tool for heterocycle synthesis. Despite impressive advances, the exploitation of new catalysis strategies and systems is still highly significant to enrich the heterocycle family. Herein, we disclosed a cooperative catalysis system merging an achiral Pd catalyst and a chiral Co catalyst for the asymmetric [4+2] cycloaddition between vinyl benzoxazinones and N-acylpyrazoles. Chiral tetrahydroquinolines bearing two contiguous, unusual cis-configured stereocenters were produced in high yields and enantio- and diastereoselectivities. The pyrazole directing group can be easily converted into many other functional groups, thus demonstrating the flexibility of the present methodology.