Selective Nucleophilic Substitutions on Tetrazines

Novàk, Zoltán; Bostai, Beatrix; Csékei, Márton; Lőrincz, Krisztián; Kotschy, András

doi:10.3987/com-03-9875

Cited by 58 publications

(4 citation statements)

References 19 publications

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“…Generally, alkyl amines are moderately nucleophilic, and therefore, they typically result in only monosubstitution on BDMPZ‐Tz . In comparison, oxygen and sulfur nucleophiles tend to be more nucleophilic and can lead to multiple substitutions on the tetrazine ring 26 . Monosubstituted amine ( DMPZ‐Tz‐NH 2 ) was synthesized by the reaction between BDMPZ‐Tz and ammonia in toluene.…”

Section: Resultsmentioning

confidence: 99%

“…In comparison, oxygen and sulfur nucleophiles tend to be more nucleophilic and can lead to multiple substitutions on the tetrazine ring. 26 Monosubstituted amine (DMPZ-Tz-NH 2 ) was synthesized by the reaction between BDMPZ-Tz and ammonia in toluene. The synthesis of the homogeneous Ru (II) complexes of BDMPZ-Tz [Ru-1] and DMPZ-Tz-NH 2 [Ru-2] involved reacting their respective ligands with [Ru( p-cym)Cl 2 ] 2 in methanol, under a temperature of 85 C for 6 h using reported procedure (Scheme 2).…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

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Sustainable and selective transfer hydrogenation using waste shrimp shell‐based tetrazene‐Ru (II) para‐cymene catalyst with ethanol as a hydrogen source

Patil,

Shelte,

Biradar

et al. 2023

Applied Organom Chemis

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Sustainable chemical research emphasizes chitosan‐based catalysts and the need to explore the direct utilization of waste shrimp shells, whereas the use of ethanol as a hydrogen source in transfer hydrogenation is less explored due to its unfavorable redox potential, higher energy barriers, generation of reactive intermediates, and catalyst poising via metal carbonyl species or decarbonylation. Herein, we disclosed an efficient synthetic approach, conducted at ambient temperature, for surface functionalization of waste shrimp shells with 3‐(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐1,2,4,5‐tetrazine (DMPZ‐Tz) via nucleophilic substitution using 3,6‐bis(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐1,2,4,5‐tetrazine (BDMPZ‐Tz). This method results in a color change and a 75% increase in surface nitrogen content, eliminating the need for multiple syntheses and harsh reaction conditions. We utilized the strong coordination property between DMPZ‐Tz and [Ru(p‐cym)Cl2]2/RuCl3.3H2O to develop ruthenium‐embedded transfer hydrogenation catalysts supported on shrimp shells. These catalysts were employed for the selective transfer hydrogenation of unsaturated carbonyl/aldehydes to saturated carbonyl/alcohols, utilizing ethanol as the hydrogen source and potassium carbonate as the base. The performance, selectivity, and reusability of the catalyst were thoroughly assessed through spectroscopic studies, in‐situ monitoring of the reaction progress, initial rate kinetics, and control experiments. The obtained results strongly indicated that the anchoring of DMPZ‐Tz played a crucial role in achieving superior performance compared with catalysts synthesized without it or utilizing its homogeneous counterparts. The catalyst exhibits efficient reactivity, selectivity, and broad substrate scope.

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis and Characterizationmentioning

confidence: 99%

Sustainable and selective transfer hydrogenation using waste shrimp shell‐based tetrazene‐Ru (II) para‐cymene catalyst with ethanol as a hydrogen source

Patil,

Shelte,

Biradar

et al. 2023

Applied Organom Chemis

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“…After solvent removal, pure 1 h was obtained as an orange‐red viscous oil (140 mg, 94%). 1 H NMR (400 MHz, CDCl 3 ) δ 3.76 (q, J =7.1 Hz, 4H, 2CH 2 ), 1.27 (t, J =7.1 Hz, 6H, 2CH 3 ) [53] . 13 C NMR (101 MHz, CDCl 3 ) δ 159.8 (C), 159.1 (C), 42.8 (2CH 2 ), 12.5 (2CH 3 ).…”

Section: Methodsmentioning

confidence: 99%

One‐Pot and Two‐Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D‐Labeled Derivatives

Ledovskaya

Polynski

Ananikov

2021

Chemistry An Asian Journal

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Acetylene surrogates are efficient tools in modern organic chemistry with largely unexplored potential in the construction of heterocyclic cores. Two novel synthetic paths to 3,6‐disubstituted pyridazines were proposed using readily available acetylene surrogates through flexible C2 unit installation procedures in a common reaction space mode (one‐pot) and distributed reaction space mode (two‐chamber): (1) an interaction of 1,2,4,5‐tetrazine and its acceptor‐functionalized derivatives with a CaC2−H2O mixture performed in a two‐chamber reactor led to the corresponding pyridazines in quantitative yields; (2) [4+2] cycloaddition of 1,2,4,5‐tetrazines to benzyl vinyl ether can be considered a universal synthetic path to a wide range of pyridazines. Replacing water with D2O and vinyl ether with its trideuterated analog in the developed procedures, a range of 4,5‐dideuteropyridazines of 95–99% deuteration degree was synthesized for the first time. Quantum chemical modeling allowed to quantify the substituent effect in both synthetic pathways.

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“…Simple s -tetrazines are deeply colored, weakly basic compounds that can behave as reversible oxidizers and readily accept electrons, forming stable anion radicals. Being highly electron-deficient, s -tetrazines are prone to nucleophilic attack at the carbon atom (with S, N, O nucleophiles) and more rarely at nitrogen (with active C-nucleophiles). Besides normal aromatic nucleophilic substitution at carbons, the S N (ANRORC) mechanism becomes operative, for example, in the Chichibabin hydrazination of monosubstituted s -tetrazines .…”

Section: Introductionmentioning

confidence: 99%

Three-Component Reaction of 3,3-Difluorocyclopropenes, s-Tetrazines, and (benzo) Pyridines

Nechaev¹,

Cherkaev

Boev³

et al. 2020

J. Org. Chem.

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A new three-component reaction leading to 1-α-(pyridyl-2-[1,2,4]triazolyl)-2-alkyl-ethanones has been discovered while studying the reactivity of monosubstituted 3,3-difluorocyclopropenes in an inverse electronic demand Diels−Alder (IEDDA) cycloaddition−cycloreversion sequence with s-tetrazines. The reaction involving the above-mentioned reactants and (benzo)pyridine as a third component results in a complex transformation proceeding in mild conditions in a stoichiometric ratio of reactants and has high functional group tolerance (phenols, amides, ethers, carboxylic acids, ketones, and acrylic esters). As a result, simple pyridines are selectively functionalized at the α-position in good isolated yields. The reaction mechanism includes a rare azaphilic [4 + 2]cycloaddition step between s-tetrazine and intermediate 1-hydroxyindolizine, suggested after byproduct identification and tracked with a deuterium label. To date, it is only the third known example of skewed azaphilic cycloaddition of tetrazine. The reaction is truly three-component and cannot be effectively performed stepwise.

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Selective Nucleophilic Substitutions on Tetrazines

Cited by 58 publications

References 19 publications

Sustainable and selective transfer hydrogenation using waste shrimp shell‐based tetrazene‐Ru (II) para‐cymene catalyst with ethanol as a hydrogen source

Sustainable and selective transfer hydrogenation using waste shrimp shell‐based tetrazene‐Ru (II) para‐cymene catalyst with ethanol as a hydrogen source

One‐Pot and Two‐Chamber Methodologies for Using Acetylene Surrogates in the Synthesis of Pyridazines and Their D‐Labeled Derivatives

Three-Component Reaction of 3,3-Difluorocyclopropenes, s-Tetrazines, and (benzo) Pyridines

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