A convenient synthesis of isonitriles has been devised using a N, N-dimethylformamide (DMF) solution of chlorodimethylformiminium chloride, prepared in situ from t, hionyl chloride and DMF, to dehydrate a variety of formamides. This general procedure enables one to prepare aliphatic, alicyclic, vinylic, and aromatic isonitriles in excellent yields. The reduction of isocyanates with lithium tri-tert-butoxylaluminum hydride to yield formamides is ...