Abstract
Homo- and bishomoallylic secondary and tertiary amines react with Rh(I) complexes di-μ-chloro(tetracarbonyl)dirhodium(I) [(CO)2RhCl]2 (1), di-μ-chloro(diethylene)(dicarbonyl)dirhodium(I) [(CO)(CH2CH2)RhCl]2 (2), or di-μ-chloro(tetraethylene)dirhodium(I) [(CH2CH2)2RhCl]2 (11) to yield bidentate mono- or dimeric complexes. The facial selectivity of binding is influenced by the presence of stereogenic centers on the tether between the alkene and amine. 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 supports the expected syn addition across the alkene and carbonylation with retention of configuration. Reaction of allylic dideutero-substituted bishomoallylamine co...
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