An atom-economical and efficient olefination strategy for ketones is described. Ethoxyacetylide addition followed by a gold-catalyzed Meyer-Schuster rearrangement affords α, β-unsaturated esters, generally in excellent overall yield from the starting ketones. The alkynophilicity of Au3+ promotes an interaction with the electron-rich acetylenes that catalyzes the Meyer-Schuster rearrangement selectively over other conceivable pathways.
