Catalytic Carbonylation and Carboxylation of Organosulfur Compounds via C−S Cleavage

Abstract

Transition‐metal‐catalyzed carbonylation with CO gas occupies a privileged position in organic synthesis for the synthesis of carbonyl compounds. Although this attractive and useful chemistry has led many researchers to investigate carbonylative transformations of various organic (pseudo)halides, C−S‐cleaving carbonylation of organosulfur compounds has been fairly limited. Recently, a broad spectrum of C−S‐cleaving transformations has been emerging in the field of cross‐coupling. In light of the importance of carbonyl compounds as well as considerable advancement for employing organosulfur compounds as competent surrogates of (pseudo)halides, carbonylative transformations of C−S bonds should be of high value. This Minireview focuses on catalytic C−S carbonylation of organosulfur compounds with CO or its equivalents. In addition, reductive carboxylation of C−S bonds with CO2 is described.

Generation of Organozinc Reagents from Arylsulfonium Salts Using a Nickel Catalyst and Zinc Dust

“…We are interested in the development of catalytic reactions of organosulfur compounds via the cleavage of the C–S bond. − Recently, we have reported the nickel-catalyzed carboxylation of arylsulfonium salts using zinc powder with carbon dioxide . This study implied that an arylzinc species is the intermediate formed prior to the carboxylation event, although tangible evidence for this hypothesis had been elusive or deemed unlikely in nickel-catalyzed carboxylation reactions, which use a metallic reductant.…”

Catalytic Transformations of Sulfonium Salts via C‐S Bond Activation

“…Whereas such sulfur‐containing products are useful on their own, transformations of the carbon–sulfur bonds in the products would lead to significantly expanding the utility of the products as synthetic intermediates that are equivalent to organic halides. Along this line, my group has been indeed working to develop transition‐metal‐catalyzed transformations of organosulfur compounds via C−S bond cleavage including cross‐coupling reactions [3c,e,g,h,4,5] . However, we always felt it fairly difficult to catalytically cleave C−S bonds of neutral organosulfur compounds such as sulfides and sulfoxides.…”

Electrochemical Reduction of 4‐Nitrobenzyl Phenyl Thioether for Activation and Capture of CO2

“…There has been growing interest in activation and cleavage of the carbonÀ sulfur bond due to its role in the field of fuel, coal industry, bioorganic and synthesis for decades. [1][2][3] There are many ways to activate and cleave CÀ heteroatom bonds, such as with transition metals. [4,5] However, this chemistry requires high loading of toxic and air-sensitive transition metals and extremely high temperatures and is only feasible with more reactive methyl and ethyl esters.…”

“…There has been growing interest in activation and cleavage of the carbon−sulfur bond due to its role in the field of fuel, coal industry, bioorganic and synthesis for decades [1–3] . There are many ways to activate and cleave C−heteroatom bonds, such as with transition metals [4,5] .…”