DMSO‐Assisted K3PO4‐Catalyzed Cooperative Metal‐Free, Base‐Free Etherification of Chloroheteroarenes at Low Temperature

Etherification of chloroheteroarenes was performed at low temperatures under metal‐free, ligand‐free and base‐free conditions, that is, the reaction is promoted by the cooperative effect of DMSO (solvent) as a promoter and K3PO4 providing the catalytic surface (rather than a base). The protocol exhibits good substrate scope under mild reaction conditions and has also been explored mechanistically. A highly active metal‐free etherification protocol is reported enabling the formation of the C−O bond under mild conditions (30–60 °C) with good substrate scope, thus allowing phenols, alkyl, allyl, benzyl and propargylic alcohols to be coupled efficiently with different chloroheteroarenes.