Nucleophile Promoted Functionalization of Cross‐Conjugated Enynone Gives Sulfonylated Furan

Serendipitous formation of sulfonylated furan was observed when cross‐conjugated sulfonyl enynones were reacted under basic conditions in alcohol, with solvent acting as a nucleophile. Fluorinated alcohols gave the best outcomes. Not only alcohols but other nucleophiles also worked well via Michael addition/alkyne to allene isomerization/ oxa ‐Michael addition reaction sequence. The developed protocol is extended to the synthesis of pyrrole, benzofuran, and polyheterocyclic compounds. The TFE‐substituted sulfonylated furan can be easily transformed into bi‐/triaryl methanes.