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.