Esters of N-acylated amino acids and the sterically demanding phosphine 2-(di- ortho-tolylphosphino)phenol react within 1 h at room temperature with the Rh(I) centers of [Cl(μ-Cl)Rh(cyclooctene) 2] 2 to give products of oxidative addition of the ester carbonyl–O bond. The N-acyl carbonyl oxygen is bound to the Rh in these initial adducts, but is displaced upon addition of PMe 3, PhPMe 2, NH 2NMe 2, or the thioether function of a methionine derivative. Remarkably, both initial products from achiral amino acids and their ligand adducts are formed as single five-coordinate diastereomers in essentially quantitative yields. However, asymmetric induction by chiral amino acid derivatives of proline and phenylalanine on the stereochemistry at Rh was modest. Finally, the identities of infrared absorptions of acyl and amide groups in the complexes were established unequivocally by synthesis and spectroscopy of N-acetylglycine esters with a 13C label at either the ester or amide carbonyl group.