Diastereodivergent Parallel Kinetic Resolution of Racemic 2-Substituted Pyrrolidines via Iridium-Catalyzed C(sp³)-H Borylation

Chiral 2,5-disubstituted pyrrolidines are ubiquitous subunits in natural products, bioactive compounds, pharmaceuticals, and chiral catalysts. However, their asymmetric synthesis still presents a formidable challenge. We herein report a rare example of diastereodivergent parallel kinetic resolution of racemic 2-substituted pyrrolidines via C(sp³)-H borylation. A vast array of enantioenriched cis- and trans-2,5-disubstituted pyrrolidines were obtained with high enantioselectivities. The synthetic utility was demonstrated by downstream transformations, including the synthesis of optically active pyrrolidine 197B and cis-pyrrolidine 225H.