Synthesis of linear O-aryl carbamates and S-thiocarbamates via benign T3P-mediated condensation of phenols and thiols with amines and carbon dioxide.

Linear (thio)carbamates are important molecules in agrochemical and pharmaceutical contexts. However, their synthesis typically involves the use of toxic reagents. Here, we present a benign method to synthesize O-aryl carbamates starting from phenols, primary amines, carbon dioxide and a peptide coupling reagent propanephosphonic acid anhydride (T3P) at atmospheric CO2 pressure and room temperature. The scope was extended to thiols, yielding aryl- and alkyl S-thiocarbamates under similarly mild conditions.