Upgrading CO2 by Incorporation into Urethanes through Silver-Catalyzed One-Pot Stepwise Amidation Reaction

One-pot two-step stepwise reaction of terminal propargylic alcohols, carbon dioxide, and primary/secondary amines for the effective synthesis of various urethanes through robust silver-catalysed C-O/C-N bond formation is reported. Catalytic activities were investigated by controlling catalyst loading, reaction pressure and time, and very high turnover number (turnover frequency) was obtained: 3350 (35 h(-1)) with 0.01 mol% silver catalyst under 0.1 MPa, and up to 13360 (139 h(-1)) with 0.005 mol% silver catalyst under 2.0 MPa at room temperature. The strategy was ingeniously regulated, and synchronously afforded a wide range of -oxopropylcarbamate and 1,3-oxazolidin-2-one motifs in excellent yields and selectivity together with unprecedented high turnover number (TON) and turnover frequency (TOF) value.