Indium(III)-Catalyzed Synthesis of Primary Carbamates and N-Substituted Ureas

An indium triflate-catalyzed synthesis of primary carbamates from alcohols and urea as an ecofriendly carbonyl source has been developed. Various linear, branched, and cyclic alcohols were converted into the corresponding carbamates in good to excellent yields. This method also provided access to N-substituted ureas by carbamoylation of amines. All the products were obtained by simple filtration or crystallization, without the need for chromatographic purification. Mechanistic investigations suggest that the carbamoylation reaction proceeds through activation of urea by O-coordination with indium, followed by nucleophilic attack by the alcohol or amine on the carbonyl center of urea. The inexpensive and easily available starting materials and catalyst, the short reaction times, and the ease of product isolation highlight the inherent practicality of the developed method.

Automated summary

An eco-friendly method for the synthesis of primary carbamates from alcohols and urea using indium triflate as catalyst has been developed. The reaction provides good to excellent yields of carbamates from various alcohols and allows for the synthesis of N-substituted ureas from amines. The mechanism involves urea activation by indium through O-coordination, followed by nucleophilic attack by alcohols or amines.