Sulfoxonium Ylides as Carbene Precusors in Rhodium‐Catalyzed Sommelet‐Hauser Rearrangement for the Synthesis of S/Se‐Containing Compounds

Rhodium-catalyzed Sommelet-Hauser rearrangement derived from α-thioesters/α-selenoesters and sulfoxonium ylides has been developed for the synthesis of various sulfur/selenium-containing ortho-substituted aromatic compounds in medium to excellent yields (39 examples; up to 97%). Sulfoxonium ylides as the safe carbene precursors are first used in Sommelet-Hauser rearrangement reactions, which is superior to traditional diazo compounds. The present reaction has the advantages of mild condition, safety and broad substrate scope, which afford a unique method for the synthesis of sulfur/selenium-containing compounds with a tertiary carbon centre.