1,3-Dipolar cycloaddition of azomethine ylides and electron deficient alkenes is widely studied for rapid installation of pyrrolidine frameworks. Despite significant advances, the major limitations of this process are creating chiral pyrrolidines bearing a quaternary stereogenic center and controlling the diastereoselectivity. Herein, we present an exo-selective asymmetric 1,3-dipolar cycloaddition to access chiral pyrrolidines with four contiguous stereogenic centers, including a fluorinated quaternary stereogenic center at C4, wherein a Cu(OAc)2/(S)-tol-BINAP catalyst and α-fluoro-α,β-unsaturated arylketone dipolarophiles are used. Epimerization promoted by 5.0 equiv of DBU at 90 °C results in the formation of chiral 4-fluoropyrrolidines (exo') while maintaining the optical purity.