Silver-Promoted Decarboxylative Sulfonylation of Aromatic Carboxylic Acids with Sodium Sulfinates

Abstract

A novel and efficient synthesis of sulfones was developed via a silver-promoted decarboxylative sulfonylation reaction between aromatic carboxylic acids and sodium sulfinates for the first time. The approach features operational simplicity and good functional group compatibility and uses readily available starting materials. Furthermore, mechanistic studies reveal that the decarboxylative sulfonylation reaction is likely to proceed via a radical mechanism.

Oxidative Sulfonylation of Multiple Carbon‐Carbon bonds with Sulfonyl Hydrazides, Sulfinic Acids and their Salts

“…[157] The reaction of benzoic acids with sodium sulfinates in the presence of Ag 2 CO 3 also led to diaryl sulfones. [158] p-Dimethoxybenzene 299 was effectively sulfonylated with a wide range of sodium and lithium aryl, hetaryl, and alkyl sulfinates 298 under the action of manganese triacetate in HFIP at room temperature (Scheme 131a), while a mixture of regioisomers 302 and 303 was formed from 2-methyl-4-methoxyanisole…”

“…Visible light photoredox‐catalyzed synthesis of diaryl sulfones and arylalkyl sulfones in 48–95% yields from aromatic diazonium salts and aromatic or aliphatic sodium sulfinates in MeCN−H 2 O under an inert atmosphere was developed with the use of eosin Y as the photocatalyst [157] . The reaction of benzoic acids with sodium sulfinates in the presence of Ag 2 CO 3 also led to diaryl sulfones [158] …”

Recent Progress in Sulfonylation via Radical Reaction with Sodium Sulfinates, Sulfinic Acids, Sulfonyl Chlorides or Sulfonyl Hydrazides

“…A silver-promoted decarboxylative sulfonylation reaction between aromatic carboxylic acids and sodium sulfinates was achieved by Zhu group. [51] Preliminary mechanism investigations revealed that the reaction probably proceeded via a radical pathway. In the reaction mechanism, silver not only provided the sulfonyl radical via oxidation of sodium sulfinate, but also assisted the decarboxylation of aromatic carboxylic acid (Scheme 41).…”

“…A silver‐promoted decarboxylative sulfonylation reaction between aromatic carboxylic acids and sodium sulfinates was achieved by Zhu group [51] . Preliminary mechanism investigations revealed that the reaction probably proceeded via a radical pathway.…”

Electrochemical study of 4-chloroaniline in a water/acetonitrile mixture. A new method for the synthesis of 4-chloro-2-(phenylsulfonyl)aniline and N-(4-chlorophenyl)benzenesulfonamide

“…In addition, the oxidation of sulphides and sulfoxides are efficient methods for the synthesis of diaryl sulfone. 29,30 In addition, diaryl sulfones were synthesized by Nicatalysed photoredox sulnylation of halides, 31 cross coupling of aryl iodide with sulnate salts in the presence of photoredox/ Ni catalyst, 32 Cu-catalyzed direct sulfonylation of indolines, 33 silver-promoted decarboxylative sulfonylation of aromatic carboxylic acids with sodium sulnates, 34 arenes and 3CdSO 4 -$xH 2 O in the presence of P 2 O 5 via mechanochemistry 35 and electrochemical methods. [36][37][38] All of these methods are efficient in synthesis of diaryl sulfones.…”