Complexes [AuCl{C(NHR)(NHR')}] and [AuCl{C(NHR)(NEt2)}] (R =Bu-t, p-Tol, Xylyl, p-C6H4-COOH, p-C6H4COOEt, R' = Me, Bu-n, Pr-i, (n)heptyl, p-Tol) have been prepared by reaction of the corresponding isocyanogold complexes [AuCl(CNR)] with either primary amines or diethylamine. All the prepared carbenes are reactive and highly selective catalysts for skeletal rearrangement, methoxycyclization of 1,6-enynes, and other mechanistically related gold-catalyzed transformations. Overall, these easily accessible nitrogen acyclic carbene (NAC) gold complexes were not second to NHC complexes and were advantageous to obtain different products.