Ethyl‐2‐Cyano‐2‐(2‐Nitrophenylsulfonyloximino)Acetate (ortho‐NosylOXY) Mediated One‐Pot Racemization Free Synthesis of Ureas, Carbamates, and Thiocarbamates via Curtius Rearrangement

Direct conversion of carboxylic acids to ureas, carbamates, and thiocarbamates in a single pot via Curtius rearrangement is accomplished. One recently established coupling reagent, Ethyl‐2‐cyano‐2‐(2‐nitrophenylsulfonyloximino)acetate (ortho‐NosylOXY, I), is successfully used for the racemization free synthesis of ureas, di‐peptidyl ureas, and carbamates with moderate to good yield (82–69%). This single‐pot hassle‐free procedure works with a diverse range of N‐protecting groups Fmoc, Boc, and Cbz. Various amine, including aromatic, methyl esters of amino acids, t‐butylamine, alcohols, and thiols, are used as nucleophiles. A detailed NMR‐based mechanism study is incorporated here. Racemization suppression, easy removal of by‐products, and less waste generation make this methodology useful. A convenient racemization‐free method for urea, carbamate, and thiocarbamate synthesis using ethyl‐2‐cyano‐2‐(2‐nitrophenylsulfonyloximino)acetate (ortho‐NosylOXY) is described.