Regio- and Diastereoselective Dimerization of Diazo Carbonyls: A Cooperative Catalytic Approach to Complex Scaffolds with Four Contiguous Stereocenters.

Starting from readily available o-diazoacyl-substituted arene carboxylates, scaffolds with the 5,9-epoxycyclohepta[b]pyran-2(3H)-one core were obtained by cooperative RhII , Lewis and Brønsted acid catalysis. Four new bonds, three functional groups (lactone, ketal, and alcohol) and four contiguous stereocenters are formed during this regio- and diastereoselective process in a single synthetic step. Intensive optimization and mechanistic studies, including the trapping, isolation, and elucidation of reaction intermediates, led to a plausible mechanistic scenario. The reaction is proposed to involve carbonyl ylides but also transient species of the ketocarbene equilibrium that undergo a cascade of cycloaddition and skeletal rearrangements.