Cu-catalyzed deaminative thiocyanation of anilines via nitrate reduction.

An efficient protocol for the synthesis of aryl thiocyanates from anilines and KSCN by merging nitrate reduction with copper-catalysis has been developed. The combination of inexpensive Fe(NO3)3·9H2O and Na2S2O3·5H2O enabled a safe and green diazotization of anilines. The fleeting diazonium salts reacted with KSCN rapidly to afford the aryl thiocyanates in good to excellent yields using Cu(OTf)2 as the catalyst. The operational simplicity and safety, good substrate scope and scalability highlight the synthetic significance of this protocol.