A catalytic asymmetric synthesis of 8-oxabicyclo[3.2.1]octane derivatives was achieved through the [3+2]-cycloaddition of the platinum-containing carbonyl ylides generated from acyclic gamma,delta-ynones on treatment with 10 mol % of PtCl2-Walphos and AgSbF6. Synthetically useful 8-oxabicyclo[3.2.1]octane derivatives were obtained in good yields and mostly in over 90% ee's.