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.

In recent years, gold catalysis involving Au(I)/Au(III) redox cycle has gained significant attention. This account summarizes our contributions in the development of Au(I)/Au(III) catalysis focusing on cross-coupling reactions and 1,2-difunctionalization reactions of C-C multiple bonds. A special emphasis has been given towards understanding the mechanism of the reactions.