The regioselectivity of the sulfonylation of tetrazoles: a theoretical view

Liu, Chenchen; Qiao, Bolin; Qu, Lingbo; Zhang, Tao; Li, Shi-Jun; Lan, Yu

doi:10.1039/d2qo00797e

Cited by 7 publications

(2 citation statements)

References 54 publications

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“…Recently, Liu et al have performed a DFT calculations to study the regioselectivity of sulfonylation of tetrazoles [44]. They considered N 2 as a leaving group, and proposed another electron transfer pathway for tetrazole reactions, which is accompanied by denitrogenating and the formation of a dipolar nitrile imine species.…”

Section: Resultsmentioning

confidence: 99%

Unveiling the zwitterionic and stepwise mechanism for the domino reactions of amidine with 1,2,4,5‐ and 1,2,3,5‐tetrazines

Haghdadi

Hamzehloueian

2022

Int J of Quantum Chemistry

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The mechanisms of the domino reactions between 4,6-diphenyl-1,2,3,5-tetrazine (TTZ 1) and 3,6-diphenyl-1,2,4,5-tetrazine (TTZ 2) with amidine 3, have been studied at the M06-2X/6-311G(d,p) level of theory. The domino reactions of TTZ1 with amidine comprise three consecutive reactions, an aza Diels-Alder (ADA) reaction with a stepwise mechanism, a retro Diels-Alder (rDA) reaction, and an amine elimination process, which leads to the resulting aromatic triazine ring. However, the most favorable pathway for domino reaction of the amidine with TTZ2 consists of nucleophilic addition, N 2 elimination, and cyclization steps which is deal with the formation of a neutral intermediate. The N 2 loss step in both mechanisms is spontaneously, with extremely exergonic formation of the corresponding intermediates. Finally, NH 3 is removed through an irreversible intramolecular elimination. The global electron density transfer (GEDT) calculations unleash the polar natures of the first step of the reactions.

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Section: Resultsmentioning

confidence: 99%

Unveiling the zwitterionic and stepwise mechanism for the domino reactions of amidine with 1,2,4,5‐ and 1,2,3,5‐tetrazines

Haghdadi

Hamzehloueian

2022

Int J of Quantum Chemistry

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“…Tetrazoles (CN 4 H 2 ) belong to a five-membered heterocyclic class consisting of the highest nitrogen content among the stable heterocycles and have undergone extensive research over a period of more than 130 years. , Tetrazoles and their derivatives exhibit three important characteristics of novelty, diversity, and complexity in terms of electronic structures, which can therefore be used as advantageous intermediates with broad applications in many fields, such as biochemistry, photographic industry, agriculture, coordination chemistry, explosives based on their high-energy properties, and medicinal chemistry in particular. − Interestingly, the tetrazole family can undergo tautomeric transformations to produce a predominant 1H or 2H tautomer, − which is sensitive to different types of environmental matrices and may also involve migrations of substituent groups. − Finally, and perhaps the most important, the rich photochemistry of tetrazoles is strongly influenced by the nature of substituents in tetrazolic rings, which acts as a versatile strategy broadening their applications in synthesis.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Understanding and Reactivity Analyses for the Photochemistry of Disubstituted Tetrazoles

Yang

Liang

et al. 2023

J. Phys. Chem. A

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The photolysis of tetrazoles has undergone extensive research. However, there are still some problems to be solved in terms of mechanistic understanding and reactivity analyses, which leaves room for theoretical calculations. Herein, multiconfiguration perturbation theory at the CASPT2//CASSCF level was employed to account for electron correction effects involved in the photolysis of four disubstituted tetrazoles. Based on calculations of vertical excitation properties and evaluations of intersystem crossing (ISC) efficiencies in the Frank–Condon region, the combination of space and electronic effects is found in maximum-absorption excitation. Two types of ISC (1ππ* → 3nπ*, 1ππ* → 3ππ*) are determined in disubstituted tetrazoles, and the obtained rates follow the El-Sayed rule. Through mapping three representative types of minimum energy profiles for the photolysis of 1,5-, and 2,5-disubstituted tetrazoles, a conclusion can be drawn that the photolysis of tetrazoles exhibits reactivity characteristic of bond-breaking selectivity. Kinetic evaluations show that the photogeneration of singlet imidoylnitrene operates predominately over that in the triplet state, which can be confirmed by a double-well model in the triplet potential energy surface of 1,5-disubstituted tetrazole. Similar mechanistic explorations and reactivity analyses were also applied to the photolysis of 2,5-disubstituted tetrazole to unveil fragmentation patterns of nitrile imine generation. All computational efforts allow us to better understand the photoreactions of disubstituted tetrazoles and to provide useful strategies for regulating their unique reactivity.

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A novel Cu complex coated on hercynite magnetic nanoparticles as an efficient and recoverable nanocatalyst for the selective synthesis of tetrazoles

Ghasemirad,

Norouzi,

Moradi

2024

J Nanopart Res

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The regioselectivity of the sulfonylation of tetrazoles: a theoretical view

Abstract: DFT calculations were performed to reveal the regioselectivity for the sulfonylation of tetrazoles. By comparing the substituent effect of tetrazoles, we found that the regioselectivity depends mainly on the steric...

Cited by 7 publications

References 54 publications

Unveiling the zwitterionic and stepwise mechanism for the domino reactions of amidine with 1,2,4,5‐ and 1,2,3,5‐tetrazines

Unveiling the zwitterionic and stepwise mechanism for the domino reactions of amidine with 1,2,4,5‐ and 1,2,3,5‐tetrazines

Mechanistic Understanding and Reactivity Analyses for the Photochemistry of Disubstituted Tetrazoles

A novel Cu complex coated on hercynite magnetic nanoparticles as an efficient and recoverable nanocatalyst for the selective synthesis of tetrazoles

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