The transition metal-catalyzed trimethylenemethane [3+2] cycloaddition provides a direct route to functionalized heterocycles. Herein, we describe a catalytic, asymmetric protocol for the reaction between 3-acetoxy-2-trimethylsilylmethyl-l-propene and various imines. The corresponding pyrrolidines were obtained in excellent yields and enantioselectivities making use of the novel phosphoramidite L10.