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

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.

Automated summary

The cooperative catalysis system of an achiral Pd catalyst and a chiral Co catalyst was used for the asymmetric [4+2] cycloaddition, yielding chiral tetrahydroquinolines with high yields and enantio- and diastereoselectivities. The flexibility of the methodology was demonstrated by the easy conversion of the pyrazole directing group into various other functional groups.