Basicity‐Controlled Reactivity of meta‐OTf‐Substituted Diaryliodonium Salts for Direct Arylation or Diels‐Alder Cycloaddition of Pyrrole Derivatives

Abstract In this study, we explored the reactivity of meta ‐trifluoromethanesulfonate (OTf) substituted diaryliodonium salts under alkaline conditions. Two distinct pathways with direct arylation of pyrrole derivatives and Diels‐Alder cycloaddition via aryne intermediates, have been found upon the relative alkalinity strength of potassium carbonates or hydroxides. This approach offers a straightforward and efficient route to synthesize heterocyclic aromatics under mild reaction conditions with tolerance of various functional groups.