A transition-metal-catalyze denantioselective 1,3-dipolar cycloaddition reaction between alkenes and nitrones has been developed employing 10 mol % of a chiral titanium catalyst generated in situ from Ti(i-OPr)(2)Cl-2 and chiral diols. Diastereofacial discrimination in favor of the exo isomer was achieved in up to a 95:5 ratio. Isoxazolidines with an optical purity of up to 62% ee are obtained from this reaction. By precipitation of a racemate of one of the isoxazolidines an optical purity of >95% ee is obtained.