Copper‐Catalyzed Sequential Azomethine Imine‐Alkyne Cycloaddition and Umpolung Thiolation Reactions

Zhang, Min; Wu, Feifei; Wang, Huanhong; Wu, Junshi; Chen, Wanzhi

doi:10.1002/adsc.201700387

Cited by 15 publications

(7 citation statements)

References 36 publications

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“…In the absence of firm experimental and theoretical proofs, the generally accepted plausible mechanism is based on the catalytic Cu(I) acetylide as the reactive species, which undergoes cycloaddition, followed by protonation of the cuprated cycloadduct. 22,24,28,29,31,[33][34][35]37,38,42,45,46 This reaction pathway is supported by experiments performed with copper(I) acetylides, deuterated acetylenes, and/or proton sources, such as D 2 O and AcOD. 29,[33][34][35]38 Copper(I) was, either used directly, 29,33 or formed in situ by reduction of Cu(II) 34,35 or by oxidation of Cu(0).…”

Section: The Mechanism Of the Cuaiac Reactionmentioning

confidence: 92%

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Copper-Catalyzed Azomethine Imine–Alkyne Cycloadditions (CuAIAC)

Grošelj

Požgan²,

Štefane³

et al. 2018

Synthesis

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Although the first example of copper-catalyzed azomethine imine–alkyne cycloaddition (CuAIAC) was published only a year after the seminal papers of Meldal and Sharpless on Cu-catalyzed azide–alkyne cycloaddition (CuAAC), the CuAIAC reaction has remained overlooked by the synthetic community for almost a decade. Since 2010, however, CuAIAC reaction started to emerge as a promising supplement to the well-known CuAAC reaction. The present review surveys primarily the literature on CuAIAC reaction since 2003. Beside this, azomethine imine–alkyne cycloadditions catalyzed by other metals, selected examples of metal-free reactions, and related [3+3] and [3+4] cycloadditions of azomethine imines are presented. All these experimental data indicate the viability of CuAIAC in organic synthesis and the applicability in ‘click’ chemistry.1 Introduction2 Reactions with Acyclic Azomethine Imines3 Reactions with C,N-Cyclic Azomethine Imines4 Reactions with N,N-Cyclic Azomethine Imines5 Reactions with C,N,N-Cyclic Azomethine Imines6 The Mechanism of the CuAIAC Reaction7 Conclusions and Outlook

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Section: The Mechanism Of the Cuaiac Reactionmentioning

confidence: 92%

“…is proposed to proceed via the cuprated bicyclic pyrazolidinone intermediate 63, which undergoes electrophilic thiolation with p-toluenesulfonothioate (Scheme 19). 31…”

Section: Syn Thesismentioning

confidence: 99%

Copper-Catalyzed Azomethine Imine–Alkyne Cycloadditions (CuAIAC)

Grošelj

Požgan²,

Štefane³

et al. 2018

Synthesis

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“…Xu reported a copper‐catalyzed click reaction of alkynes ( 269 ) and azides ( 304 ) in which the triazolyl‐copper complex intermediate 306 was intercepted by S ‐aryl/alkyl benzenethiosulfonate ( 7 ) electrophiles (Scheme ) . A similar 1,3‐dipolar cycloaddition between azomethine imines ( 307 ) and alkynes ( 269 ) generates a pyrazolidinonate‐copper intermediate 309 , which was trapped by S ‐alkyl/aryl benzenethiosulfonates ( 7 ) to generate N , N ‐bicyclic pyrazolidiones ( 308 ) (Scheme ) . ( o ‐Alkynylaryl) sulfides ( 311 ) were prepared by Xu via a copper‐catalyzed three‐component coupling of terminal alkynes ( 269 ), thiosulfonates ( 7 ) and in situ formed arynes (Scheme ) .…”

Section: Applications Of Thiosulfonates In Synthesismentioning

confidence: 99%

Thiosulfonates as Emerging Reactants: Synthesis and Applications

et al. 2019

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The synthetic strategies towards thiosulfonates (RSO2SR1) are comprehensively reviewed from their original discovery to recent advances. Incorporation of the green credentials of the synthetic procedures towards thiosulfonates allows one to judge the merits of the state of the art, beyond the typical yield of a product and availability of the reactants. As reactant for organic transformations, thiosulfonates are particularly interesting given their possibility to react with nucleophiles, electrophiles and radicals. This review aims to give researchers, not familiar with the field, a good understanding of the general applications of thiosulfonates, while not skipping the recent important advances. The related, but less explored, selenosulfonates (RSO2SeR1) are also covered.

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“…a thiosulfonate. 9 Thus, we tried to trap the possible intermediate by adding phenyl thiosulfonate either at the beginning of the reaction or after two hours, but in both cases no other reaction product 14 was formed. Alternatively, bromine was added to the reaction mixture to form vinyl bromide 15, but again no product 15 was observed.…”

Section: Trapping Experiments For the Elucidation Of The Reaction Mechanismmentioning

confidence: 99%

Synthesis of 1-Aza-6,7-dehydrotropanes via Copper(I)-Catalyzed Coupling of 5-Chloropentan-2-one with Hydrazines and Terminal Alkynes

Beek

Weemaes

Herrebout

et al. 2018

Synlett

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A one-pot, three-component, Cu(I)-catalyzed coupling of primary hydrazines, 5-chloropentan-2-one, and terminal alkynes was developed. The resulting 1-aza-6,7-dehydrotropanes compose a new class of substances while related 1-azatropanes are scarcely described in literature and closely resemble tropane alkaloids. Hydrogenation of the double bond in 1-aza-6,7-dehydrotropanes triggered a rearrangement, involving a [1,3]-hydride shift, forming cyclic hydrazones.

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Copper‐Catalyzed Sequential Azomethine Imine‐Alkyne Cycloaddition and Umpolung Thiolation Reactions

Cited by 15 publications

References 36 publications

Copper-Catalyzed Azomethine Imine–Alkyne Cycloadditions (CuAIAC)

Copper-Catalyzed Azomethine Imine–Alkyne Cycloadditions (CuAIAC)

Thiosulfonates as Emerging Reactants: Synthesis and Applications

Synthesis of 1-Aza-6,7-dehydrotropanes via Copper(I)-Catalyzed Coupling of 5-Chloropentan-2-one with Hydrazines and Terminal Alkynes

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