Catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides with dimethyl itaconate and 2-methyleneglutarate was realized with the Cu(I)/TF–BiphamPhos complex as the catalyst for the efficient construction of pyrrolidine derivatives bearing one unique all carbon-quaternary and two tertiary stereogenic centers. The current catalytic system exhibited excellent diastereoselectivity (> 20 : 1), good enantioselectivity (88–>99% ee) and broad substrate scope under mild conditions.