Theoretical insight into the mechanisms of the synthesis of chiral gold(I)–aminocarbene complexes

Abstract By using density functional theory calculations, we studied the reaction mechanisms to synthesize chiral gold(I)-aminocarbene complexes through a cyclization–rearrangement cascade. Our calculated results show that the mechanism containing a [3,3]-sigmatropic rearrangement process is more favorable compared with the 1,2-alkyl shift, which can be attributed to the steric effects. By investigating the transition state structures related to the rate-determining step, we conclude that the yield of product is mainly controlled by the steric effects of the different substituent groups.