Biomimetic building-up of the carbamic moiety: The intermediacy of carboxyphosphate analogues in the synthesis of N-aryl carbamate esters from arylamines and organic carbonates promoted by phosphorus acids

Article abstract of DOI:10.1016/0040-4020(95)00424-7

The reaction of aromatic amines with dimethyl carbonate (DMC) or diphenyl carbonate (DPC) in the presence of organo-phosphorus acids [Ph₂P(O)OH (1); (PhO)₂P(O)OH (2); (BuO)₂P(O)OH/(BuO)P(O)(OH)₂ equimolar mixture (3)] affords carbamate esters, ArNHC(O)OR (R = Me, Ph) with high selectivity. The catalytic role played by the P-acid has been investigated and rationalized in terms of a reaction mechanism involving the intermediate formation of a carbonic-phosphinic(phosphoric) anhydride X₂P(O)OC(O)OR (X = Ph, PhO; R = Me, Ph). The proposed mechanism shows intriguing analogies with the mechanism of formation of carbamate anion in living systems by carbamoyl phosphate synthetase (CPS) enzyme. Copyright