A cationic gold(I)-catalyzed asymmetric [3,3]-sigmatropic rearrangement of sulfonium leads after cyclization to cyclopentenones with a C4-quaternary stereocenter. Starting with simple vinyl sulfoxides and propargyl silane, numerous compounds were isolated with moderate to good yields and excellent enantiomeric excesses (26 examples). The application of this simple methodology allowed the efficient total synthesis of five natural sesquiterpenoids, including enokipodin A and B, hitoyopodin A, lagopodin A, and isocuparene-3,4-diol.