Computational Mechanistic Study of Bronsted Acid-Catalyzed Unsymmetrical 1,2,4,5-Tetrazines Synthesis

Cui Xianlu; Ding Chengxiang; Zhang Congcong; Jiao Zixian; Zhang Lixiong; Zhao Xuefei; Zhao Lili

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Computational Mechanistic Study of Bronsted Acid-Catalyzed Unsymmetrical 1,2,4,5-Tetrazines Synthesis

机译：富抗酸催化的非对称1,2,5-四嗪合成的计算机械研究

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Density functional theory (DFT) calculations were conducted to gain insight into the reaction mechanism of the Bronsted acid-catalyzed unsymmetrical 1,2,4,5-tetrazine synthesis. Various possible reaction pathways were considered, and the most favorable one can be characterized via sequential six steps, including addition of DCM to hydrazine 1 giving complex IM4, N-H bond activation in IM4 mediated by sulfur, AcOH-assisted substitution of 3 with sulfur-activated hydrazine 2, HNO2-assisted addition of nitrile to intermediate 8, cyclization, and intramolecular elimination leading to the final product 7. Among the six steps, sulfur activation of IM4 N-H bond is found to be the ratedetermining step (RDS). The mechanism rationalizes the experimental observation that 2 equiv of sulfur leads to the best yield of product. Furthermore, we disclosed that the Bronsted acid additives (i.e., acetic acid and nitrous acid) served triple roles as catalyst, proton shuttle, and hydrogen bond donor and acceptor in the whole catalysis.

机译：通过密度泛函理论（DFT）计算，深入了解了Bronsted酸催化不对称合成1,2,4,5-四嗪的反应机理。考虑了各种可能的反应途径，最有利的反应途径可以通过连续六个步骤进行表征，包括向肼1中添加DCM，生成复合物IM4，通过硫介导IM4中的N-H键活化，AcOH辅助用硫激活的肼2取代3，HNO2辅助向中间体8中添加腈，环化，分子内消除最终产物7。在这六个步骤中，IM4 N-H键的硫活化是速率决定步骤（RDS）。该机理使实验观察结果合理化，即2当量的硫可以获得最佳的产品收率。此外，我们还发现，Bronsted酸添加剂（即乙酸和亚硝酸）在整个催化过程中起着催化剂、质子穿梭器和氢键供体和受体的三重作用。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2021年第22期|共12页
作者
Cui Xianlu; Ding Chengxiang; Zhang Congcong; Jiao Zixian; Zhang Lixiong; Zhao Xuefei; Zhao Lili;
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Nanjing Tech Univ Sch Chem &

Mol Engn Inst Adv Synth Nanjing 211816 Peoples R China;

Nanjing Tech Univ Sch Chem &

Mol Engn Inst Adv Synth Nanjing 211816 Peoples R China;

Nanjing Tech Univ Sch Chem &

Mol Engn Inst Adv Synth Nanjing 211816 Peoples R China;

Nanjing Tech Univ Sch Chem &

Mol Engn Inst Adv Synth Nanjing 211816 Peoples R China;

Nanjing Tech Univ Coll Biotechnol &

Pharmaceut Engn Nanjing 211816 Peoples R China;

Nanjing Tech Univ Sch Chem &

Mol Engn Inst Adv Synth Nanjing 211816 Peoples R China;

Nanjing Tech Univ Sch Chem &

Mol Engn Inst Adv Synth Nanjing 211816 Peoples R China;

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正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
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Computational Mechanistic Study of Bronsted Acid-Catalyzed Unsymmetrical 1,2,4,5-Tetrazines Synthesis

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