Iron/Copper Co-Catalyzed Synthesis of Vinyl Sulfones from Sulfonyl Hydrazides and Alkyne Derivatives

Abstract

A new approach to the selective synthesis of (E)-vinyl sulfones has been developed via a Fe/Cu co-catalyzed sulfonylation of arylpropiolic acid or phenylacetylene with sulfonyl hydrazides. A variety of vinyl sulfones have been obtained in moderate to good yields, comparable to the best results reported so far. The inexpensive Fe/Cu co-catalyzed method features a simple experimental procedure and good tolerance of substrate.

Recent advances in the synthesis of vinyl sulfones

“…22 Several alkyl and halo substituted aryl alkynes and heterocyclic alkynes, furnished the reactions smoothly affording the desired products in moderate to good yields, with exclusively E isomers obtained (Scheme 8). And the reaction was believed to mechanistically proceed via sulfonyl radical addition/reductive elimination pathway.…”

“…Very recently, encouraged by Mao and Zhang' work, 22 Kuhakarn and co-workers 62 reported Na 2 CO 3 -promoted decarboxylative sulfonylation of arylpropiolic acids with arylsulfinic acids in the absence of a transition metal catalyst (scheme 37). This simple and environmentally benign transformation offers an alternative approach and allows for easy and rapid synthesis of (E)-vinyl sulfones.…”

The Application of Copper/Iron Cocatalysis in Cross-Coupling Reactions

“…[32] After a thorough exploration of the reaction conditions, the combination of copper acrylate and FeCl 2 Á4H 2 O in the presence of tert-butyl peroxide was found to be the most effective catalyst. Sulfonyl hydrazides and alkyne derivatives bearing a series of substituents on the phenyl ring were suitable substrates, providing the expected vinyl Scheme 10.…”

“…Iron/copper cocatalytic synthesis of vinyl sulfones reported by Mao. [32] Scheme 16. Iron/copper cocatalytic photochemical C-H borylation reported by Mazzacano and Mankad.…”

Generation of β‐Halo Vinylsulfones through a Multicomponent Reaction with Insertion of Sulfur Dioxide

“…Usually,s ulfonyl halides/selenides/azides/cyanides/hydrazides, sulfinates, and sulfinic acids were utilized in the sulfonylative processthroughr eductive or oxidative approaches. [3,4] Recently,u sing sulfur dioxide as the sourcef or the introduction of the sulfonyl unit into small molecules has been employed as ar eplacement. [5] For example,c omparedt ot he conventionala pproaches by using sulfonyl compounds for the synthesis of 3-sulfonatedc oumarins, [6] the strategy throughinsertion of sulfur dioxide in aradical process for introducing the sulfonyl group was successfully established under more mild condition.…”