An efficient, solvent-free protocol for the N-fluorenylmethoxycarbonylation and N-benzyloxycarbonylation of amines is described. The reaction of aliphatic and aromatic amines with FmocOSu and Cbz-Osu in [Bmim]-[BF 4 ] at room temperature afforded the corresponding N-urethane derivatives in excellent yields and do not require any further purification. The method has been extended to the N-Fmoc and N-Cbz protection of amino acids. Absence of bases, very short reaction times, high yields, selectivity and ease of product separation are some advantages of this protocol. ; Fax: +39 0984 493265; Tel: +39 0984 493095, +39 0984 493205 † Electronic supplementary information (ESI) available: Copy of 1 H and 13 C NMR spectra for compounds 3a-o and 4a-o. See