We demonstrate the iron-catalyzed
intermolecular coupling of internal alkynes and thiosalicylic acid
derivatives. The reaction was effectively catalyzed by the Fe(acac)2/1,10-phenanthroline catalyst in toluene/HFIP (hexafluoroisopropyl
alcohol) as the reaction solvent and afforded several types of 1,3-oxathiine
derivatives in moderate to high yields through the intermolecular
hydrothiolation and sequential intramolecular cyclization.