The enantioselective intermolecular gold(I)- catalyzed [2+2] cycloaddition of terminal alkynes and alkenes has been achieved using non C2-chiral Josiphos digold(I) com- plexes as catalysts, by the formation of the monocationic com- plex. This new approach has been applied to the enantioselec- tive total synthesis of rumphellaone A.