Reaction scope. The scope of the reaction was examined using the optimized reaction conditions. At first, different N-arylpyrrolidines 1a-f were examined (Scheme 5). The reaction works well with psubstituted N-arylpyrrolidines leading to 3a-3d in 42-57% yield and good levels of diastereoselectivity in favor of the α isomer (α/β ≥5:1). The relative configuration of the 3a was determined by single crystal X-ray diffraction crystallography. Interestingly, the electron rich N-p-methoxyphenylpyrrolidine required longer reaction time despite the fact that this compound is more easily oxidizable, indicating that the critical step of the reaction is probably the deprotonation of the radical cations leading to the α-aminoalkyl radicals as discussed by Mariano in his early work (see a discussion of the mechanism, vide infra). In this particular case, the use of the slightly more basic CsOPiv instead of CsOAc provided 3d in a good 56% yield. The presence of ortho-substituent proved to be more problematic as shown by the long reaction time and low yield (20%) observed for the formation of 3e.