Addition of anhydrous HCl to the complex at −78 °C followed by P(OMe)3 in MeOH yields lactams from secondary amine complexes or amino esters from reaction of the corresponding tertiary amine complexes in a highly stereoselective fashion. Isolation of intermediate Rh(III) alkyls 21−23 or Rh(III) acyls 24 or 25 upholds the proposed mechanistic hypothesis. Reaction with a trisubstituted alkenylamine