An efficient asymmetric aza-Diels-Alder reaction using chiral boron mediator is developed. The key to its success is the use of the chiral boron complex prepared in situ from (R)-or (S)- binaphthol and B (OPh) 3. The enantiomeric reaction of prochiral imine affords products of up to 90% ee. The double asymmetric induction of chiral imine using α-benzylamine as a chiral auxiliary is achieved with almost complete diastereoselectivity for both aliphatic and ...