Electrochemically Promoted C−N Bond Formation from Amines and CO2 in Ionic Liquid BMIm−BF4:  Synthesis of Carbamates

A new electrochemical procedure for the synthesis of organic carbamates from amines and carbon dioxide has been developed using selective cathodic reduction of carbon dioxide in CO2-saturated room-temperature ionic liquid BMIm-BF4 solutions containing amines 1a−j, followed by addition of EtI as an alkylating agent. The synthesis was carried out under mild (P CO 2 = 1.0 atm, t = 55 °C) and safe conditions, and the use of volatile and toxic solvents and catalysts (according to the growing demand for ecofriendly synthetic methodologies), as well as of any supporting electrolyte (for a very easy workup of the reaction mixture), was avoided. Carbamates 2a − j were isolated in good to high yields.