Ah ighly regio-and stereoselective method to construct ab road range of 7-oxabicyclo[2.2.1]heptanes, which proceeds throughasequential reactioni nvolving gold(I)-catalyzed cycloisomerization of alkynediols and sequential semi-pinacol-type1 ,2-alkyl migration,w as developed. The developed chemistry was applied to the asymmetric total synthesis of the natural product farnesiferol C.