Copper-Catalyzed Decarboxylative Disulfonylation of Alkynyl Carboxylic Acids with Sulfinic Acids

Abstract

A copper-catalyzed decarboxylative disulfonylation of alkynyl carboxylic acids with sulfinic acids in aqueous solution has been developed. The reaction provides a straightforward and practical access to (E)-1,2-disulfonylethenes, which are important building blocks in synthetic organic chemistry, and exhibits a good functional group tolerance and excellent stereoselectivity. A possible mechanism for the transformation is proposed.

Cs2CO3‐Mediated Vicinal Thiosulfonylation of 1,1‐Dibromo‐1‐Alkenes with Thiosulfonates: An Expedient Synthesis of (E)‐1,2‐Thiosulfonylethenes

“…elegantly reported a gold/photoredox‐cocatalyzed vicinal thiosulfonylation of alkynes using PhSO 2 SR (R=CF 3 and CF 2 H) as a diheterofunctionalization reagent (Scheme b) . Very recently, Li group employed a copper‐catalyzed decarboxylative disulfonylation of alkynyl carboxylic acids with sulfinic acids to form ( E )‐1,2‐disulfonylethenes (Scheme c) . These approaches usually require an expensive metal catalyst(s), excess use of oxidants and inaccessible starting materials.…”

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

“…[119] When the reaction of aryl and hetarylpropiolic acids 209 with aryl, hetaryl, and alkylsulfinic acids 210 was conducted in DMSOÀ H 2 O mixture under an inert atmosphere in the presence of the Cu(ClO 4 ) 2 • 6H 2 O/ (NH 4 ) 2 S 2 O 8 system, the formation of 1,2-disulfonylethenes 211 as a result of addition of two sulfonyl moieties was observed (Scheme 95). [120] The same products were synthesized via CuI-catalyzed sulfonylation of terminal alkynes with sodium sulfinates. [121] The process runs through the generation of sulfonyl radical A under oxidative conditions, its successive addition to the generated copper acetylenide B with the formation of vinyl radical C. Recombination of C with sulfonyl radical A and subsequent proton quenching of the resulting intermediate D leads to the desired product 211 (Scheme 96).…”

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

“…Decarboxylative coupling is one of the most powerful tools to construct C−C and C‐heteroatom bonds [74] . In 2018, a copper‐catalyzed decarboxylative disulfonylation of alkynyl carboxylic acids with sulfinic acids in aqueous solution was described by Li group [75] . Various of (E)‐1,2‐disulfonylethenes were isolated using this method.…”