in situ Formation of RSCl/ArSeCl and Their Oxidative Coupling with Enaminone Derivatives Under Transition‐metal Free Conditions

The reaction of diorganyl disulfides or diselenides with PhICl2 in DMF at room temperature led to the in situ formation of the reactive organosulfenyl chloride (RSCl) or selenenyl chloride (ArSeCl), which reacted with enaminone compounds to afford a series of α‐thioenaminones or α‐selenylenaminones, respectively, including the bioactive inhibitor for Cdc25B and its analogue, via the intermolecular oxidative C(sp2)‐S/Se cross coupling reactions under metal‐free conditions.