KI-mediated radical multi-functionalization of vinyl azides: a one-pot and efficient approach to β-keto sulfones and α-halo-β-keto sulfones

Sulfonyl hydrazides are widely used as organic reagents. Advances in the past decade are summarized in the following categories by key intermediates: (1) [RO2S.]; (2) RO2SSR; (3) [ArS.]; (4) [RO2S−]; (5) RSO2‐[Metal] species; (6) Ar‐[Metal] species; (7) RSX; (8) RS‐DBU; (9) nucleophilic amino group; (10) sulfonyl hydrazides as diazene or sulfinic acid surrogate. Reactions with alkenes, alkynes, aldehydes, alcohols, thiophenol, Grignard reagents, among others, are discussed. We hope this review will promote future research in this area.

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“…Yu and co‐workers utilized vinyl azides as starting materials in the construction of β ‐keto sulfones (Eq. 21‐1).…”

Section: Sulfonyl Radiacls‐mediated Reactionsmentioning

confidence: 99%

Sulfonyl Hydrazides in Organic Synthesis: A Review of Recent Studies

et al. 2020

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“…One year later in 2017, Yu et al [88] reported a transition metal-free, reagent-controlled oxosulfonylation reaction between vinyl azides and sulfonyl hydrazines. According to this radical process, a mixture vinyl azides 35a, sulfonyl hydrazines 35b in DMSO was kept on stirring in presence of KI as an additive and TBHP as a radical initiator at 25°C to achieve β-keto sulfones 35c in 70-90% yields (Scheme 35).…”

Section: In Alkene Systemmentioning

confidence: 99%

Advances in Oxosulfonylation Reaction

et al. 2020

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Oxosulfonylation is a difunctionalization protocol where oxo and sulfonyl groups are introduced in one step to construct ketosulfones and Nacylsulfonamides from simple and readily accessible reagents. The development of oxosulfonylation methods has gained significant attention due to their importance in organic and medicinal chemistry. This review article provides a brief and concise overview of the current status and latest methodologies using green oxidant and sulfonyl sources for oxosulfonylation reactions developed in the last two decades.

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“…78 In a similar vein, sulfonyl hydrazines have been shown to be a valuable source of sulfonyl radicals in the KI/tert-butyl hydroperoxide-mediated oxidative coupling with vinyl azides (Scheme 34). 79 Further reaction of the resulting βketo sulfones 141 with the corresponding potassium halide under acidic conditions affords α-halo-β-keto sulfones 142, through putative intermediates 143. Very recently, a convenient and functional-group tolerant silver(I)-catalyzed aminosulfonylation reaction has been developed by our group, using readily available terminal alkynes, TMSN 3 as an ammonia source, and sodium sulfinates as a sulfonyl source (Scheme 35a reaction proceeds through a sequence of silver-catalyzed alkyne hydroazidation, followed by attack of the sulfonyl radical onto the in situ generated vinyl azide.…”

Section: Reduction Of 131 By Mes-acrmentioning

confidence: 99%

α-Substituted vinyl azides: an emerging functionalized alkene

et al. 2017

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Vinyl azides are highly versatile synthons that provide access to numerous N-heterocycles and other functional groups. α-Substituted vinyl azides (azido vinylidenes) are a special class that display unique reactivity, able to react not only as azides, but also as radical acceptors, enamine-type nucleophiles, and even electrophiles, thus delivering a wide range of nitrogen-containing compounds and their derivatives. An impressive variety of intermediates - such as iminodiazonium ions, nitrilium ions, iminyl radicals, and metal enaminyl radicals - can be generated from vinyl azides and exploited in cycloadditions, C-H functionalizations, hydrolysis processes, and cascade reactions under transition metal/photoredox catalysis. In addition to presenting synthetic protocols to access vinyl azides, this Review offers a comprehensive coverage of the development of their multifaceted reactivity, and highlights their potential as versatile precursors for synthetic applications.

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KI-mediated radical multi-functionalization of vinyl azides: a one-pot and efficient approach to β-keto sulfones and α-halo-β-keto sulfones

Abstract: Transition metal-free oxidative coupling of vinyl azides with sulfonyl hydrazines is described.

Cited by 63 publications

References 48 publications

Sulfonyl Hydrazides in Organic Synthesis: A Review of Recent Studies

Sulfonyl Hydrazides in Organic Synthesis: A Review of Recent Studies

Advances in Oxosulfonylation Reaction

α-Substituted vinyl azides: an emerging functionalized alkene

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