Terminal Alkyne Addition to Diazodicarboxylates: Synthesis of Hydrazide Linked Alkynes (Ynehydrazides)

Beveridge, Ramsay E.; Batey, Robert A.

doi:10.1021/ol2031608

Cited by 38 publications

(26 citation statements)

References 64 publications

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“…4b,22,36 Additions of the alkylnyllithium intermediates to ethyl chloroformate gave 61 and 63 in 90% and 47% yield, respectively. A particularly interesting example is the S N 2 methylation of the phosphoramidate-derived ynamide 64 to the farnesol derivative 65 which produced a mixture of bicyclic enamine 66 and tricyclic imine 67 upon heating (Scheme 16).…”

Section: Nucleophilic Addition and Substitution Reactionsmentioning

confidence: 99%

Terminal ynamides: synthesis, coupling reactions, and additions to common electrophiles

Cook

Wolf

2015

Tetrahedron Letters

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Ynamides consist of a polarized triple bond that is directly attached to a nitrogen atom carrying a sulfonyl, an alkoxycarbonyl, an acyl or another electron withdrawing group. The triple bond polarization renders ynamides broadly useful building blocks with synthetic opportunities that go far beyond traditional alkyne chemistry. The versatile reactivity of ynamides in cycloadditions, cycloisomerizations, regioselective additions with various nucleophiles or electrophiles, ring-closing metathesis, and many other reactions has been investigated in detail during the past decades. A common feature of these methods is that the triple bond is consumed and either cleaved or transformed to a new functionality. The wealth of reports on these ynamide reactions is in stark contrast to the dearth of carbon-carbon bond formations that leave the triple bond of terminal ynamides intact. The recent introduction of effective synthetic methods for the preparation of terminal ynamides has set the stage to fully explore the synthetic potential of this intriguing class of compounds. This digest letter summarizes the most effective routes to terminal ynamides and the current state of selective nucleophilic addition, substitution and coupling reactions, including the first examples of asymmetric synthesis.

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Section: Nucleophilic Addition and Substitution Reactionsmentioning

confidence: 99%

Terminal ynamides: synthesis, coupling reactions, and additions to common electrophiles

Cook

Wolf

2015

Tetrahedron Letters

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“…Fortunately, internal alkyne containing hydrazines were found to be able to undergo regioselective Ru-catalyzed cycloaddition of azide with alkyne to yield substituted hydrazine 1,2,3-triazole 121 and then the resulting heterocycle was rapidly transformed into an unusual N-1,2,3-triazole functionalized 1,2,4-triazole 122 (54%) by simple addition of formamide and anhydrous hydrogen chloride (Scheme 49). Further work displayed that these heterocyclic systems would be difficult to disconnect via alternative chemistry which demonstrated the significant promise of ynehydrazines for the preparation of N-linked bis-heterocycles [170].…”

Section: Cyclizations Of Hydrazinesmentioning

confidence: 99%

Current Developments in the Syntheses of 1,2,4-Triazole Compounds

Zhang¹,

Damu²,

Cai³

et al. 2014

COC

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Heterocyclic 1,2,4-triazole derivatives possess unusually spacious potentiality as medicinal agents, agricultural chemicals, functional materials, ionic liquids, supramolecular catalysts as well as artificial enzymes and receptors for supramolecular recognition and biomimetic catalysis, and their various researches and developments have been being a quite rapidly developing and active highlight topic with an infinite space. Numerous efforts have been directed toward various types of possible applications of 1,2,4-triazole-based compounds and a lot of important progress has been made, especially their preparations have attracted increasing attention. This review systematically summarized the recent advances in the syntheses of 1,2,4-triazole derivatives, including: (1) Cyclizations to form triazole ring; (2) Transformations of heterocyclic compounds to construct triazole ring; (3) Substitutions on 1,2,4-triazole ring; (4) Structural modifications in side chains of 1,2,4-triazole ring. It was hoped that this review would be helpful for the design and development of highly efficient preparation of 1,2,4-triazole derivatives with various sorts and varieties of extensively potential applications in medicine, agriculture, chemistry, materials, supramolecular sciences and so on.

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“…Very recently, preparations of structural analogues of ynamides have emerged as novel N-containing alkyne building blocks. [27][28][29][30][31][32][33][34][35][36] These preparations mainly are based on modified methods for ynamide synthesis [22][23][24][25][26] as described in Scheme 1. With the belief that these novel analogues will also become versatile synthons that will be tremendously useful to organic synthesis, especially in the arena of N-heterocycle constructions, we highlight herein syntheses and reactions of de novo ynamide analogues: diaminoacetylenes 2, ynimides 3, yne-imines 4, yne-hydrazides 5, amidinylynamides 6, and yne-sulfoximines 7 (Scheme 1).…”

Section: Introduction: Ynamide Analoguesmentioning

confidence: 99%

Novel ynamide structural analogues and their synthetic transformations

Lu¹,

Hsung²

2014

Arkivoc

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This Highlight accounts for a recent phenomenon in which a series of novel ynamide structural analogues have emerged and caught the attention of the synthetic community. Preparations and reactions of these de novo ynamide variants are delineated here to demonstrate their accessibility as well as their reactivity. This Highlight should help reveal that these unique N-containing alkynes can become highly versatile building blocks in organic syntheses.

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Terminal Alkyne Addition to Diazodicarboxylates: Synthesis of Hydrazide Linked Alkynes (Ynehydrazides)

Cited by 38 publications

References 64 publications

Terminal ynamides: synthesis, coupling reactions, and additions to common electrophiles

Terminal ynamides: synthesis, coupling reactions, and additions to common electrophiles

Current Developments in the Syntheses of 1,2,4-Triazole Compounds

Novel ynamide structural analogues and their synthetic transformations

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