Gold‐catalysed generation of diol equivalents from epoxides and their intramolecular reaction with C≡C bonds to generate bicyclic ketals is presented. This reaction essentially involves the formation of an acetonide, which subsequently cyclises on the alkyne intramolecularly under gold catalysis conditions. This method could be extended to make optically pure bicyclic ketals. Deuterium incorporation experiments were carried out to ascertain the mechanism of the reaction.

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Regioselective hydration of α‐alkynyl esters and ketones by using a cationic NHC–AuI catalyst results in β‐keto esters and β‐diketones, respectively. Controlled release of water in acetone by aldol self‐condensation under the reaction conditions makes acetone as better solvent than 1,4‐dioxane/water for the hydration of α‐alkynyl esters having sensitive ester moieties.

A highly efficient chiral-at-metal Rh(iii) complex catalyzed asymmetric aza-Michael addition was developed, affordingN-protected β-amino acid derivatives with excellent enantioselectivity.