Copper-catalyzed multicomponent cascade synthesis of polyfunctionalized β-ketone sulfones

Abstract

The multicomponent cascade reaction provides an efficient paradigm for the preparation of complex compounds in synthetic chemistry. Herein, we describe a copper-catalyzed multicomponent cascade of vinyl azides, oxime esters with...

Recent advances in ring-opening of cyclobutanone oximes for capturing SO2, CO or O2via a radical process

“…They described a copper-catalyzed radical cascade reaction of vinyl azides 27 , oxime esters 1 and Na 2 S 2 O 5 for the synthesis of polyfunctionalized β-ketone sulfones (Scheme 11). 51 Based on the control experiment results, a series of processes were involved in this transformation such as radical relay, radical addition, hydrogen abstraction, and hydrolysis or oxidation. More importantly, a one-pot four-component radical cascade reaction, which directly utilizes the terminal alkyne and TMSN 3 instead of the vinyl azide reaction with oxime esters and Na 2 S 2 O 5 , can also generate the corresponding desired β-ketone sulfone products in moderate yields.…”

Advances in Vinyl Sulfone Catalyzed Synthesis: Methods, Mechanisms and Perspectives

“…In addition to the low price, copper catalysts typically have the advantages of low toxicity, mild chemistry and simple ligands, so catalytic systems involving copper salts are also a hot field. [42][43][44] Recently, Li and co-workers have chosen copper as the catalyst and not only demonstrated its excellent catalytic performance, but also innovatively used ethylbenzene instead of conventional alkenes and alkynes as the vinyl source to successfully construct the vinyl sulfone backbones (Scheme 3). [45] In the exploration of alkene elimination dehydrogenation, they proposed a one-pot approach to construct functionalized styrene derivatives and based on this, a series of (E)-vinyl sulfones were obtained by continuous N-sulfonylbenzo [d]imidazole in the presence of copper(I) catalyst, with a moderate to a good yield of approximately 75 %.…”

Nickel-Catalyzed Reaction between Vinyl Azides and an Alkyl Sulfonyl Radical Generated from DMSO: Rapid Access to β-Keto Sulfones

“…34−37 Notably, a series of reactions using sulfonyl hydrazines as the source of sulfonyl radicals to react with vinyl azides for the preparation of β-keto sulfones have been reported. 28,29,38,39 In 2023, our group has developed a copper-catalyzed multicomponent cascade reaction for the synthesis of β-keto sulfones from vinyl azides, oxime esters, and Na 2 S 2 O 5 . 28 Although remarkable progress has been achieved in the reaction between sulfonyl radicals and vinyl azides, the use of DMSO as a source of alkyl sulfonyl radical has never been mentioned.…”

“…Vinyl azides as a crucial class of synthons have received extensive attention from organic chemists in chemical synthesis. − In this context, the addition reactions of vinyl azides with sulfonyl radicals are prominent, providing a reliable pathway to construct β-keto sulfones, enamines, phenanthridines, etc. (Scheme C). − Among them, β-keto sulfones are commonly employed as a critical synthetic building block in organic syntheses. − Notably, a series of reactions using sulfonyl hydrazines as the source of sulfonyl radicals to react with vinyl azides for the preparation of β-keto sulfones have been reported. ,,, In 2023, our group has developed a copper-catalyzed multicomponent cascade reaction for the synthesis of β-keto sulfones from vinyl azides, oxime esters, and Na 2 S 2 O 5 . Although remarkable progress has been achieved in the reaction between sulfonyl radicals and vinyl azides, the use of DMSO as a source of alkyl sulfonyl radical has never been mentioned.…”

“…28,29,38,39 In 2023, our group has developed a copper-catalyzed multicomponent cascade reaction for the synthesis of β-keto sulfones from vinyl azides, oxime esters, and Na 2 S 2 O 5 . 28 Although remarkable progress has been achieved in the reaction between sulfonyl radicals and vinyl azides, the use of DMSO as a source of alkyl sulfonyl radical has never been mentioned. Herein, we propose to use the stable bulk chemical DMSO as the source of an alkyl sulfonyl radical to synthesize β-keto sulfones from vinyl azides utilizing cheap and readily available NiCl 2 as the catalyst in conjunction with the green oxidant H 2 O 2 .…”