Pyrrolidines are synthetic targets of choice in organic chemistry. [1] 2,5-Substituted derivatives are particularly important motifs with relevant applications in many areas of chemistry such as catalysis and medicinal chemistry. To date, the synthesis of enantioenriched pyrrolidines mostly relies on enantioselective functional group transformations. In this context, we designed a novel approach for the streamlined synthesis of enantiopure pyrrolidines based on two sequential C(sp 3)-H functionalization reactions. The first intermolecular C(sp 3)-H amination involves a regio-and stereoselective rhodium-catalyzed nitrene C-H insertion. [2] Then, a subsequent diastereoselective cyclization operating through a 1,5-Hydrogen Atom Transfer (HAT) from a N-centered radical leads to the formation of pyrrolidines. [3] Importantly, the resulting protected pyrrolidines can be readily converted to their free NH-derivatives. [4]