The vinyl-substituted oxyallyl carbonates were exploited as a new C,O-dipole for enantioselective Pd-catalyzed (3+2) cycloaddition. The corresponding oxyallyl-Pd species was weakly nucleophilic to react with activated carbonyl compounds, affording multisubstituted and enantioenriched oxazolidinones and 1,3-dioxolanes with a high degree of chemo- and stereoselectivity. The synthetic transformations of oxazolidinone product were carried out to build enantioenriched α-chiral aminoketone and epoxy derivatives.