Metal‐Free HFIP‐Promoted Synthesis of Benzhydryl Derivatives from Stilbenes as Masked Electrophiles under Oxidative Conditions

Benzhydryl derivatives are synthesized by a new strategy involving the use of stilbenes as an electrophilic reaction partner through umpolung reactivity in a nucleophilic substitution reaction. The transformation, which requires oxidative treatment with meta ‐chloroperoxybenzoic acid and the presence of 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP) as an essential solvent and reaction promoter, occurs through multiple consecutive steps. Under these conditions, different benzhydryl derivatives are synthesized by coupling stilbenes with a variety of nitrogenated, oxygenated, and sulfur‐ and carbon‐based nucleophiles.