Copper-Catalyzed Disulfonation of Terminal Alkynes with Sodium Arylsulfinates

Abstract

A novel and direct disulfonylation reaction of commercially available terminal alkynes under copper­(I)/bromodifluoroacetate cocatalyst has been realized. This protocol provides a facile and practical pathway to selectively access (E)-1,2-disulfonylethenes, in which features good functional group compatibility, easily available starting materials, and excellent stereoselectivity with good yields.

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds

“…In 2020, Gao, Tang, and co-workers demonstrated the copper-catalyzed vicinal disulfonylation of less reactive terminal alkynes with sodium sulfinates under the influence of bromodifluoroacetate for the synthesis of ( E )-1,2-disulfonylethenes ( Scheme 106B ). 164 Various aryl and heteroaryl alkynes were disulfonylated with sodium p -toluenesulfinate to obtain a wide range of ( E )-1,2-disulfonylethenes in moderate to good yields, irrespective of their electronic and steric properties. Interestingly, eneynes were substantiated as a suitable coupling partner for the desired products in appreciable yields, whereas, there was no reaction with alkyl-derived alkynes.…”

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

“…[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).…”

“…When the reaction of aryl and hetarylpropiolic acids 209 with aryl, hetaryl, and alkylsulfinic acids 210 was conducted in DMSO−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] …”

Silver-catalyzed synthesis of β-fluorovinylphosphonates by phosphonofluorination of aromatic alkynes

“…Among the strategies for constructing diverse alkenes containing two-heteroatom bonds, such as disulfonylation [14][15][16], heterohalogenation [17][18][19][20], bis(trifluoromethyl)thiolation [21], and phosphorylation [22], the direct heterodifunctionalization of alkynes using three-component reactions is the most rapid and convenient one (Scheme 1). Although studies on alkyne difunctionalization are ongoing [23], the successful attachment of a fluorine atom to the resulting alkene through transition metal catalysis remains a challenge.…”