An effective enantioselective 6-endo bromoaminocyclization of 2,4-dienyl N-tosylcarbamates catalyzed by a chiral phosphine oxide-Sc(OTf)3 complex is described. A wide variety of optically active 5-bromo-1,3-oxazinan-2-ones containing various functional groups can be obtained in 61-91% yields and 92-99% ees. An additive, such as NaCl, has been found to be crucial for the reaction process.