AMINE-DIRECTED ALKENE HYDROCARBOXYLATION

Homo- and bishomoallylic secondary and tertiary amines react with Rh(I ) complexes di-mu-chloro(tetracarbonyl)dirhodium(I) [(CO)(2)RhCl](2) ( 1), di-mu-chloro(diethylene)(dicarbonyl)dirhodium(I) [(CO)(CH2CH2)RhCl ](2) (2), or di-mu-chloro(tetraethylene)dirhodium(I) [(CH2CH2)(2)RhCl] (2) (11) to yield bidentate mono- or dimeric complexes. The facial sel ectivity of binding is influenced by the presence of stereogenic cente rs on the tether between the alkene and amine. Addition of anhydrous H Cl to the complex at -78 degrees C followed by P(OMe)(3) in MeOH yield s lactams from secondary amine complexes or amino esters from reaction of the corresponding tertiary amine complexes in a highly stereoselec tive 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 supports the expected syn addition across the alkene and carbonylation with retention of configuration. Reaction of allylic dideutero-substituted bishomoallylamine complex 59 yielded valerolactam 70. The lack of deuterium scrambling suggested t hat pi-allyl intermediates are not present during hydrometalation and carbonylation.