In Situ Formation of RSCl/ArSeCl and Their Application to the Synthesis of 4-Chalcogenylisocumarins/Pyrones from o-(1-Alkynyl)benzoates and ( Z)-2-Alken-4-ynoates.

The reaction of diorganyl disulfides or diselenides with PhICl2 in acetonitrile was found for the first time to lead to the in situ formation of organosulfenyl chloride or selenenyl chloride, which enables the regioselective intramolecular chalcogenylacyloxylation of alkynes resulting in the formation of 4-chalcogenylisocumarins/pyrones in good to excellent yields under metal-free conditions.