Catalytic Enantioselective House–Meinwald Rearrangement: Efficient Construction of All-Carbon Quaternary Stereocenters

A catalytic asymmetric House–Meinwald rearrangement for the synthesis of both cyclic and acyclic ketones is disclosed. From readily accessible racemic tetrasubstituted epoxides, this approach provides efficient access to chiral ketones bearing α all-carbon quaternary stereocenters with high enantiocontrol. The observation of positive nonlinear effects and nontrivial kinetic feature provided important insights into the mechanism.