Gold-Catalyzed Alkynylative Meyer-Schuster Rearrangement.

By applying the "interplay" mode, which consolidates two key reactivity modes of gold catalysis, namely π-activation mode and cross-coupling mode, the first alkynylative Meyer-Schuster rearrangement is designed and successfully implemented. The current protocol gives straightforward access to enynones, a highly valuable building block, from easily available propargyl alcohol feedstocks. Control experiments suggest an Au(III) catalyst triggers the Meyer-Schuster rearrangement, whereas monitoring the reaction with ESI-HRMS provided strong evidence in favor of a key alkynylgold(III) intermediate which supports the proposed "interplay" scenario.