Ni-catalyzed asymmetric decarboxylation for the construction of carbocycles with contiguous quaternary carbon stereocenters

Abstract

The first Ni-catalyzed asymmetric decarboxylative strategy for the construction of carbocycles with contiguous quaternary all-carbon stereocenters is reported. The key to the success of these reactions is the utilization of rationally designed allenylic methylene cyclic carbonates as substrates with Ni catalysis. The floppy allenylic group exerts unique electronic properties on the carbonate, which allows further asymmetric nucleophilic annulations with alkenes. These reactions can be performed at room temperature and feature wide functional group tolerance with excellent asymmetric induction that is typically >94% ee. The mechanistic insights imply that this conceptually new chemistry is completely different from previous reports on the catalytic transformation of cyclic carbonates, and thus, it offers an inventive novel methodology to create complex enantio-enriched molecules.