The fate of the aryl gold(I) carbenes generated by retro-Buchner reaction of ortho-substituted 7-aryl-1,3,5-cycloheptatrienes is dependent on the constitution of the ortho substituent. Indenes and fluorenes are obtained by intramolecular reaction of highly electrophilic gold(I) carbenes with alkenes and arenes. According to density functional theory calculations, the gold-catalyzed retro-Buchner process occurs stepwise, although the two carbon–carbon cleavages occur on a rather flat potential energy surface.