Computational Studies of Reactions of 1,2,4,5-Tetrazines with Enamines in MeOH and HFIP

被引：5

作者：

Ma, Pengchen ^{[1
,2
,3
]}

Svatunek, Dennis ^{[3
,4
]}

Zhu, Zixi ^{[5
]}

Boger, Dale L. ^{[5
]}

Duan, Xin-Hua ^{[1
,2
]}

Houk, K. N. ^{[3
]}

机构：

[1] Xi An Jiao Tong Univ, Sch Chem, Dept Chem, Xian Key Lab Sustainable Energy Mat Chem, Xian 710049, Peoples R China

[2] Xi An Jiao Tong Univ, Engn Res Ctr Energy Storage Mat & Devices, Minist Educ, Xian, Peoples R China

[3] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

[4] TU Wien, Inst Appl Synthet Chem, A-1060 Vienna, Austria

[5] Scripps Res Inst, Dept Chem, Skaggs Inst Chem Biol, La Jolla, CA 92037 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2024年 / 146卷 / 27期

基金：

美国国家科学基金会; 美国国家卫生研究院; 中国博士后科学基金; 奥地利科学基金会; 中国国家自然科学基金;

关键词：

DIELS-ALDER REACTIONS; MOLECULAR-ORBITAL METHODS; WALLED CARBON NANOTUBES; GAUSSIAN-TYPE BASIS; CHEMICAL-MODIFICATION; DENSITY FUNCTIONALS; TETRAZINE LIGATION; ENERGIES; REACTIVITY; MODEL;

D O I：

10.1021/jacs.4c06067

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction between 1,2,4,5-tetrazines and alkenes in polar solvents proceeds through a Diels-Alder cycloaddition along the C-C axis (C3/C6 cycloaddition) of the tetrazine, followed by dinitrogen loss. By contrast, the reactions of 1,2,4,5-tetrazines with enamines in hexafluoroisopropanol (HFIP) give 1,2,4-triazine products stemming from a formal Diels-Alder addition across the N-N axis (N1/N4 cycloaddition). We explored the mechanism of this interesting solvent effect through DFT calculations in detail and revealed a novel reaction pathway characterized by C-N bond formation, deprotonation, and a 3,3-sigmatropic rearrangement. The participation of an HFIP molecule was found to be crucial to the N1/N4 selectivity over C3/C6 due to the more favored initial C-N bond formation than C-C bond formation.

引用

页码：18706 / 18713

页数：8

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