Abstract
Abstract Herein, we present a detailed investigation of the mechanistic aspects of the dual gold‐catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)} 2 (μ‐OH)][BF 4 ] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non‐coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co‐catalyst, lowering the energy barriers of several transition states. A gem ‐diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an “off‐cycle” rather than an “in‐cycle” intermediate.