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

Abstract The reaction of aromatic amines with dimethyl carbonate (DMC) or diphenyl carbonate (DPC) in the presence of organo-phosphorus acids [Ph 2 P(O)OH ( 1 ); (PhO) 2 P(O)OH ( 2 ); (BuO) 2 P(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 X 2 P(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

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