Gold‐Catalyzed 1,2‐Dicarbofunctionalization of Alkynes with Organohalides**

Abstract

Herein, we report the first gold‐catalyzed 1,2‐dicarbofunctionalization of alkynes using organohalides as non‐prefunctionalized coupling partners. The mechanism of the reaction involves an oxidative addition/π‐activation mechanism in contrast to the migratory insertion/cis‐trans isomerization pathway that is predominantly observed with other transition metals yielding products with anti‐selectivity. Mechanistic insights include several control experiments, NMR studies, HR‐MSMS analyses, and DFT calculations that strongly support the proposed mechanism.