“…One such strategy is the reaction of a sulfide with an electron-poor carbenoid intermediate to afford the desired ylide [ 55 , 71 ]. First reported by Diekmann in 1965, the photochemical decomposition of bis(phenylsulfonyl)diazomethane in sulfur-containing solvents, such as dimethylsulfide, dibutylsulfide and dimethylsulfoxide, was shown to afford ylides in moderate to good yields (Scheme 31 ) [ 72 ]. Scheme 31 Thermal versus photochemical formation of sulfonium ylides …”
Traditionally employed in the synthesis of small ring systems and rearrangement chemistry, sulfur-based ylides occupy a unique position in the toolbox of the synthetic organic chemist. In recent years a number of pioneering researchers have looked to expand the application of these unorthodox reagents through the use of transition metal catalysis. The strength and flexibility of such a combination have been shown to be of key importance in developing powerful novel methodologies. This chapter summarises recent developments in transition metal-catalysed sulfonium/sulfoxonium ylide reactions, as well as providing a historical perspective. In overviewing the successes in this area, the authors hope to encourage others into this growing field.
“…One such strategy is the reaction of a sulfide with an electron-poor carbenoid intermediate to afford the desired ylide [ 55 , 71 ]. First reported by Diekmann in 1965, the photochemical decomposition of bis(phenylsulfonyl)diazomethane in sulfur-containing solvents, such as dimethylsulfide, dibutylsulfide and dimethylsulfoxide, was shown to afford ylides in moderate to good yields (Scheme 31 ) [ 72 ]. Scheme 31 Thermal versus photochemical formation of sulfonium ylides …”
Traditionally employed in the synthesis of small ring systems and rearrangement chemistry, sulfur-based ylides occupy a unique position in the toolbox of the synthetic organic chemist. In recent years a number of pioneering researchers have looked to expand the application of these unorthodox reagents through the use of transition metal catalysis. The strength and flexibility of such a combination have been shown to be of key importance in developing powerful novel methodologies. This chapter summarises recent developments in transition metal-catalysed sulfonium/sulfoxonium ylide reactions, as well as providing a historical perspective. In overviewing the successes in this area, the authors hope to encourage others into this growing field.
“…One such strategy is the reaction of a sulfide with an electron-poor carbenoid intermediate to afford the desired ylide [55,71]. First reported by Diekmann in 1965, the photochemical decomposition of bis(phenylsulfonyl)diazomethane in sulfur-containing solvents, such as dimethylsulfide, dibutylsulfide and dimethylsulfoxide, was shown to afford ylides in moderate to good yields (Scheme 31) [72].…”
Traditionally employed in the synthesis of small ring systems and rearrangement chemistry, sulfur-based ylides occupy a unique position in the toolbox of the synthetic organic chemist. In recent years a number of pioneering researchers have looked to expand the application of these unorthodox reagents through the use of transition metal catalysis. The strength and flexibility of such a combination have been shown to be of key importance in developing powerful novel methodologies. This chapter summarises recent developments in transition metal-catalysed sulfonium/sulfoxonium ylide reactions, as well as providing a historical perspective. In overviewing the successes in this area, the authors hope to encourage others into this growing field.
“…The thermal, metal‐catalyzed, and photochemical decomposition of diazo compounds in the presence of sulfides and sulfoxides is the most frequently employed method used to prepare different types of sulfur ylides 1,27. It was first described by Diekmann28 in 1965 who reported the photochemical decomposition of bis(phenylsulfonyl)diazomethane with dibutyl sulfide and dimethyl sulfoxide (Scheme ). However, it was only after the contributions of Ando and co‐workers in 1969 and 1972 that this method received more attention 29–31.…”
Since the pioneering contribution of Corey and Chaykovsky in 1965, sulfoxonium and sulfonium ylides have proven to be versatile intermediates in organic synthesis. One of their important applications, though not yet throughly investigated, is their substitution of diazocarbonyl compounds as safer carbene precursors. This microreview provides an overview and recent applications of sulfoxonium and sulfonium ylides in inter‐ and intramolecular metal‐catalyzed insertion reactions. It also plans to illustrate the promising synthetic utility of these stable carbene precursors in industry, mitigating potential safety problems generally encountered when the equivalent diazo compounds are employed. Moreover, it aims to inspire new contributions to this exciting growing area, especially in catalytic asymmetric reactions.
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