Recent Advances in Metal‐Catalyzed C−H Bond Functionalization Reactions of Sulfoxonium Ylides

Abstract

In recent years, the transition‐metal‐catalyzed functionalization reactions of sulfoxonium ylides have been explored extensively because of their usefulness as carbene‐transfer agents, since they can produce metal carbenes through metal catalysis. Moreover, they are safer and have the advantages of simple handling and good stability over their other counterparts like diazo‐compounds. This review article attempts to highlight the recent advances in the metal‐catalyzed C−H functionalization of sulfoxonium ylides.

α-Carbonyl sulfoxonium ylides in transition metal-catalyzed C–H activation: a safe carbene precursor and a weak directing group

“…7 Sulfoxonium ylides have witnessed a renaissance in contemporary transition metal-catalyzed C–H functionalization based on carbene migratory insertion that was widely explored with diazo compounds. 8 Reaction of sulfoxonium ylides with different directing groups follows the sequence of steps that involve directing group assisted C–H activation, sulfoxonium ylide coordination followed by α-elimination of DMSO to produce metal carbene intermediate A (Scheme 1a). Then migratory insertion occurs to furnish metal–alkyl intermediate B that subsequently undergoes various transformations like protonation or cyclization to afford an assortment of products.…”

Cyclic Sulfoxonium Ylides: Synthesis and Chemospecific Reactivity in the Catalytic Alkylation of Indoles

“…Sulfoxonium ylides have recently gained renewed attention as potential surrogates of diazo compounds in both metal‐ and acid‐catalyzed reactions [1–6] . These studies have been focused on acyclic α‐carbonyl sulfoxonium ylides, whereas the potential reactivity of their cyclic congeners remains vastly unknown.…”

“…Sulfoxonium ylides have recently gained renewed attention as potential surrogates of diazo compounds in both metal-and acid-catalyzed reactions. [1][2][3][4][5][6] These studies have been focused on acyclic α-carbonyl sulfoxonium ylides, whereas the potential reactivity of their cyclic congeners remains vastly unknown. Hence, only rare examples of cyclic sulfoxonium ylides have been prepared where the sulfoxonium moiety is in an exo position to a ring.…”

Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides

“…The superior safety profile of α-carbonyl sulfoxonium ylides compared to that of their diazo counterpart has recently spurred the exploration of numerous metal-catalyzed reactions in which a metal-carbene has been proposed to be a pivotal intermediate . In this context, it is striking that enantioselective cyclopropanation of olefins by the intermediacy of a chiral metal-carbene, a hallmark of metal-carbene chemistry, has never been observed in metal-catalyzed reactions of α-carbonyl sulfoxonium ylides.…”

“…The superior safety profile of α-carbonyl sulfoxonium ylides compared to that of their diazo counterpart has recently spurred the exploration of numerous metal-catalyzed reactions in which a metal-carbene has been proposed to be a pivotal intermediate. 1 In this context, it is striking that enantioselective cyclopropanation of olefins by the intermediacy of a chiral metal-carbene, a hallmark of metal-carbene chemistry, 2 has never been observed in metal-catalyzed reactions of α-carbonyl sulfoxonium ylides. Specifically, reports of cyclopropanation of α-carbonyl sulfoxonium ylides are limited to an arene C–H activation/cyclopropanation cascade with electron-poor allenes 3 and enantioselective addition/ring closure on electron-poor olefins in the presence of either a chiral organocatalyst 4 or a chiral Lewis acid ( Scheme 1 a).…”