Highly enantioselective syntheses of (S)-2-aryl-Boc-pyrrolidines (Boc tert-butoxycarbonyl) can be achieved by treatment of the corresponding (arylmethyl)(3-chloropropyl)-Boc-amines with s-BuLi/(-)-sparteine. The reactions are solvent dependent with the phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, m-methoxyphenyl, l-naphthyl, and 2-naphthyl derivatives 1-7 providing 11-17 in yields of 46-75% with enantiomeric excesses of 84-96% in toluene. The 2-thienyl and 3-furyl analogs 8 and 9 afford the (S)-2-heteroaryl-Boc-pyrrolidines 18 and 19 in 51 and 21% yields with 93-96% enantiomeric excesses. The p-methoxyphenyl derivative 10 gives 20 as a racemic product in 42% yield under the same conditions. Reactions of nBuLi/(-)-sparteine with 1 and 8 give results comparable to those with s-BuLi/(-)-sparteine. Illustrative syntheses of (S)-2-phenyl-(S)-5-methyl-Boc-pyrrolidine (22) and 1,2-(bis-(S)-2-phenylpyrrolindyl)ethane (23) are reported. The mechanism of the reaction is shown to be an asymmetric deprotonation of 1 to give an enantioenriched organolithium intermediate (S)-24 which undergoes cyclization faster than racemization.