A 'one-flask'synthesis of guanidines was developed by reacting isocyanates and isothiocyanates with sodium bis (trimethylsilyl) amide followed by addition of primary or secondary amines with a catalytic amount of AlCl3. The desired guanidines were obtained in good yields and the reaction was applicable to aliphatic and aromatic substrates. A plausible mechanism was proposed through the generation of cyanamide anion from ...