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

Abstract

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 firstly 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 center.

Rhodium(II)-Catalyzed Hinsberg Dearomatization Using Trimethylsilyldiazomethane

“…In spite of these challenges Wang and co-workers have shown that benzyl thioethers react with rhodium and copper carbenes derived from alpha-diazoesters to generate sulfonium ylides that then undergo Hinsberg [2,3]-rearrangement (Scheme B). Similar rearrangements have been carried out using sulfoxonium ylides instead of diazo compounds . More recently, Gu and co-workers took advantage of biaryl torsional strain to facilitate the metal-catalyzed Sommelet–Hauser dearomatization of tetrahydroisoquinolines with alpha-diazoesters to generate remarkable spirocyclic trienes that are stable to silica gel chromatography (Scheme C) .…”