Copper‐Catalyzed α‐Arylation of Sulfoxonium Ylides Using Hypervalent Iodine Compounds

Abstract A Cu(I)‐catalyzed synthesis of α‐arylated sulfoxonium ylides has been achieved from mesitylene‐derived diaryliodonium salts and α‐carbonyl sulfoxonium ylides. The reaction is believed to proceed via an electrophilic Cu(III)‐aryl intermediate that can be trapped upon nucleophilic attack of the sulfoxonium ylide precursor. The reaction was tolerant to both α‐keto and α‐ester‐derived sulfoxonium ylides, to drug‐derived ylide motifs and to electronically‐diverse arenes, and enabled the direct synthesis of 32 α‐aryl‐sulfoxonium ylides in 42–85% yield.