Carbonyl compounds have been successfully converted into their corresponding dithioacetals, dithiolanes and dithianes derivatives in excellent yields with thiol (ethanethiol and thiophenol), 1,2-ethanedithiol and 1,3-propanedithiol using a catalytic amount of iodine supported on natural phosphate. In addition, by employing this catalyst, high chemoselective thioacetalization of carbonyl compounds have been achieved. (c) 2005 Elsevier B.V. All rights reserved.