Desulfonylative Electrocarboxylation with Carbon Dioxide

Abstract

Electrocarboxylation of organic halides is one of the most investigated electrochemical approaches for converting thermodynamically inert carbon dioxide (CO 2 ) into value-added carboxylic acids. By converting organic halides into their sulfone derivatives, we have developed a highly efficient electrochemical desulfonylative carboxylation protocol. Such a strategy takes advantage of CO 2 as the abundant C1 building block for the facile preparation of multifunctionalized carboxylic acids, including the nonsteroidal anti-inflammatory drug ibuprofen, under mild reaction conditions.

Recent advances in the electrochemically mediated chemical transformation of carbon dioxide

“…In 2021, Ye's group developed a highly efficient electrochemical desulfonylative carboxylation of organic sulfones with CO 2 using magnesium as a sacrificial anode under mild conditions (Scheme 18). 36 Substrates with electron-withdrawing groups and electron-donating groups on the benzene ring could go through this reaction smoothly with excellent yields. Mechanistically, the aliphatic carbon–sulfur bond of the sulfone 60 is preferentially cleaved via an overall two-electron mechanism to generate a phenylsulfinic acid ion 61 and a benzyl anion 62 .…”

A guide to organic electroreduction using sacrificial anodes

“…Besides using organic halides as precursors, the Ye group explored an electrochemical desulfonylative carboxylation using arylsulfones 112 as starting materials (Scheme 21a). 50 The corresponding benzyl anion species were directly generated from arylsulfones via a two-electron reduction approach. The reaction exhibited a broad substrate scope, and a variety of 2-phenylacetic acids 113 could be obtained under the optimized conditions, including the drug molecule ibuprofen.…”

Recent Advances in Electrocarboxylation with CO2

“…In 2021, Ye and co-workers reported a desulfonylative electrocarboxylation reaction of sulfones 71 with CO 2 to form diverse carboxylic acids 72 under mild conditions (Scheme 19, b). [57] Substituents with different electronic effects on the benzene ring were tolerated, and functionalized secondary and tertiary sulfones were also applicable to afford the carboxylation products in excellent yields. Interestingly, in the presence of multiple reaction sites of the substrates, the CÀ X bond substituted products still preferentially generated.…”