DFT Studies of Au(I) Catalysed Reactions: Anion Effects and Reaction Selectivity

Density functional theory (DFT) is a powerful tool that can aid in the exploration and development of synthetic chemistry, and its use is often applied in the chemistry of gold(I) catalysis. In this review, we discuss two different facets of these calculations – namely, the exploration and explanation of anion effects, and the regioselectivity and speciation of gold(I)‐catalysed reactions. The research described herein clearly shows the importance of including the anion in DFT studies of Au(I)‐catalysed reactions, especially when using low polarity solvents, or where hydrogen‐bonding is prevalent. Additionally, we show that whilst using DFT to study the selectivity of reactions can be successful, benchmarking the computational results against experimental data is vitally important for ensuring that the model is accurately describing the observed results.