Electrogenerated superoxide-activated carbon dioxide. A new mild and safe approach to organic carbamates

The electrochemical reduction of O-2 (E = -1.0 V vs SCE) in dipolar aprotic solvents in the presence of CO2 gave a carboxylating reagent (O-2(.-)/CO2) able to convert amines and different types of their derivatives into carbamates. Primary and secondary aliphatic and aromatic amines were converted into the corresponding ethyl carbamates by the addition of EtI to the carbamate anions generated in the first step of the reactions. The yields were dependent on the nucleophilicity of the nitrogen atom. beta-Bromoethyl- and propylamine gave 2-oxazolidinone and tetrahydro-1,3-oxazin-2-one in moderate yields. N-Acyl or N-(alkoxycarbonyl)alkylamines bearing a leaving group at the beta position of the alkyl substituent were converted into 3-substituted-2-oxazolidinones in high yields. By using chiral substrates, enantiopure 3-alkoxycarbonyl(or acyl)-4-substituted oxazolidin-2-ones (70-85% isolated yields) were obtained. This represents a new mild and safe route to these important auxiliaries for asymmetric synthesis. Some limitations of the process are also evidenced and accounted for.