In order to shed some light on a series of gold(I)-catalyzed processes, the influence of the addition of silver salts in gold(I)-catalyzed reactions has been evaluated. In addition, a new generation of gold(I) complexes containing BARF as counterion has been designed and the mechanism of the intermolecular gold(I)-catalyzed [2+2]-cycloaddition of alkynes and alkenes has been evaluated. Finally, the first enantioselective total synthesis of nardoaristolone B has been accomplished in 7 steps and 13% overall yield featuring a gold(I)-catalyzed oxidative cyclization as the key step.