Synthesis of α-cyano sulfone<i>via</i>thermal rearrangement of 1,4-disubstituted triazole mediated by carbene and radical species

Cen, Mengjie; Xiang, Qiaoyi; Xu, Yiwen; Duan, Shengguo; Lv, Yaohong; Xu, Zefeng; Li, Chuan‐Ying

doi:10.1039/c9qo01340g

Cited by 11 publications

(3 citation statements)

References 64 publications

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“…With these promising findings and considering the compatibility of ortho-substitution patterns in the aromatic ring of phenylacetylene derivatives in copper-catalyzed click chemistry, [60][61][62][63][64][65][66] we applied the same copper-catalyzed protocol from Scheme 2 to the reaction between the alkyne-containing porphyrin 1 and tosyl azide (Scheme 3). Unfortunately, the expected porphyrin product 1' did not form according to TLC, NMR and HR-MS studies.…”

Section: Resultsmentioning

confidence: 99%

Destabilizing Predictive Copper‐Catalyzed Click Reactions by Remote Interactions with a Zinc‐Porphyrin Backbone

Trouvé

Gramage‐Doria

2023

Helvetica Chimica Acta

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In order to obtain new supramolecular ligands that build up around a zinc‐porphyrin scaffold, we envisioned to access sulfonyl triazole intermediates by well‐known copper‐catalyzed click reactions. Unexpectedly, these triazole intermediates do not form due to the presence of the zinc‐porphyrin moiety at close proximity of the active copper species. Indeed, the copper catalyst undergoes a different chemo‐selective reaction pathway reacting with traces of alcohols or water from the media that behave as effective nucleophiles leading to sulfonyl imidates or sulfonyl amides covalently connected to the zinc‐porphyrin. We show that copper‐catalyzed click reactions can follow different reaction mechanisms when the catalytic events occur at close proximity of a zinc‐porphyrin unit which likely acts as a Lewis acid to stabilize otherwise inaccessible reaction intermediates.

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Section: Resultsmentioning

confidence: 99%

Destabilizing Predictive Copper‐Catalyzed Click Reactions by Remote Interactions with a Zinc‐Porphyrin Backbone

Trouvé

Gramage‐Doria

2023

Helvetica Chimica Acta

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“…However, the applicability of this protocol was limited to 1,5-disubstituted triazoles only. Later, Li and co-workers 262 disclosed the synthesis of α-sulfonylnitriles 171.4 through a thermal rearrangement of 1,4-disubstituted triazoles 171.3. A solution of the 4-substituted N-sulfonyl-1,2,3-triazole in DCE solvent was heated to 150 °C in a sealed tube to obtain the α-cyano sulfone.…”

Section: Rearrangements Involving Formation Of Keteniminesmentioning

confidence: 99%

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

2022

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Readily accessible and shelf-stable 1,2,3-triazole and its analogues such as pyridotriazole, triazoloindole, benzotriazole, and thiadiazole exist in equilibrium with their ring-opened isomers, viz., diazo compounds. These ring-opened isomers could be trapped by various metal catalysts (e.g., Rh, Pd, Cu, Co, Ag, etc.) to generate the corresponding metal carbenoids with extrusion of nitrogen. As a consequence, these unique N-heterocycles facilitate access to a realm of N-containing complex structural motifs of biological importance through denitrogenative transformations such as transannulations, insertions, ylide formation, and rearrangements by trapping of the metal carbenoids with a diverse range of coupling partners (e.g., alkenes, alkynes, nitriles, carbo/heterocycles, X–H/C–X bonds, etc.). Hence, suitably substituted triazole derivatives have emerged as efficient surrogates of diazo compounds for the generation of reactive metal carbenoids during the past decades. In this comprehensive review, we aim to discuss in detail the remarkable advancement in their synthesis and synthetic applications.

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“…Although various metal-catalyzed transformations of the N -sulfonyl-1,2,3-triazole have been well developed, 9 the usage of metal catalysts and sulfonyl groups also limits the development of 1,2,3-triazole chemistry to an extent. Studies on 1,2,3-triazole chemistry that omit the use of metal catalysts 10 or sulfonyl group substitution 11 are scarce and should be expanded to a wider range of fields (Scheme 1a).…”

Section: Introductionmentioning

confidence: 99%

Acid-catalyzed ring-expansion of 4-(1-hydroxycyclobutyl)-1,2,3-triazoles

Liu

Wang

et al. 2022

Org. Chem. Front.

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Synthesis of α-cyano sulfoneviathermal rearrangement of 1,4-disubstituted triazole mediated by carbene and radical species

Abstract: α-Cyano sulfone is produced conveniently from 1,4-disubstituted triazole, which involves carbene, ketenimine and radical species as the key intermediates.

Cited by 11 publications

References 64 publications

Destabilizing Predictive Copper‐Catalyzed Click Reactions by Remote Interactions with a Zinc‐Porphyrin Backbone

Destabilizing Predictive Copper‐Catalyzed Click Reactions by Remote Interactions with a Zinc‐Porphyrin Backbone

1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

Acid-catalyzed ring-expansion of 4-(1-hydroxycyclobutyl)-1,2,3-triazoles

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