Direct Access to Carbamates through Palladium‐Catalyzed Carbonylation of Nitroarenes and Siloxanes

A novel and applicable method for the preparation of various carbamates via a palladium‐catalyzed carbonylation reaction was developed. In the absence of fluorine sources, a wide range of nitroarenes and siloxanes are readily reacted to give the corresponding carbamates in yields ranging from 23 % to 97 % using Mo(CO)6 as both the reducing agent and the carbonyl source. Mechanistic experiments indicated that isocyanate was found to be a critical intermediate in the overall reaction. A novel and applicable method for the preparation of various carbamates via a palladium‐catalyzed carbonylation reaction was developed. In the absence of fluorine sources, a wide range of nitroarenes and siloxanes are readily reacted to give the corresponding carbamates in yields ranging from 23 to 97 % using Mo(CO)6 as both the reducing agent and the carbonyl source. Mechanistic experiments indicated that isocyanate was found to be a critical intermediate in the overall reaction.