Synthesis of 1,2,4-Triazoles via the Electrochemical Oxidative [3+2] Annulation

doi:10.6023/cjoc202011029

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (6): 2476-2484.DOI: 10.6023/cjoc202011029 Previous Articles Next Articles

Special Issue: 有机电合成虚拟专辑

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电化学脱氢[3+2]环化反应合成取代的1,2,4-三氮唑衍生物

赵志恒^a, 李鸣^a, 周娅琴^a, 何永辉^a, 张丽珠^a, 李干鹏^a, 谷利军^a^,^b^,^*()

a 云南民族大学民族医药学院民族药资源化学国家民委-教育部重点实验室昆明 650500
b 贵州大学绿色农药和农业生物工程教育部重点实验室贵阳 550025

收稿日期:2020-11-23 修回日期:2021-01-24 发布日期:2021-02-22
通讯作者: 谷利军
基金资助:
国家自然科学基金(21662045); 贵州大学绿色农药和农业生物工程教育部重点实验室开放基金(2018GDGP0103)

Synthesis of 1,2,4-Triazoles via the Electrochemical Oxidative [3+2] Annulation

Zhiheng Zhao^a, Ming Li^a, Yaqin Zhou^a, Yonghui He^a, Lizhu Zhang^a, Ganpeng Li^a, Lijun Gu^a^,^b()

a Key Laboratory of Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission & Ministry of Education, School of Ethnic Medicine, Yunnan Minzu University, Kunming 650500
b Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang 550025

Received:2020-11-23 Revised:2021-01-24 Published:2021-02-22
Contact: Lijun Gu
Supported by:
National Natural Science Foundation of China(21662045); Opening Foundation of the Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University(2018GDGP0103)

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Abstract

1,2,4-Triazoles, standing for a class of five-membered nitrogenous heterocyclic compounds, show anti-inflam- matory, anti-fungal and other biological activities. They also served as important intermediates in organic synthesis. Thus, the pursuit of general and efficient synthesis of 1,2,4-triazoles that controls the introduction of substituents in a highly regioselective fashion has been of continued interest to synthetic organic chemists. In this paper an electrochemical dehydrogenative [3+2] annulation used for the synthesis of 1,2,4-triazoles from cheap and readily available amines and hydrazones was developed. Their structures were confirmed by ¹H NMR, ¹³C NMR and HRMS analyses. Advantageously, this method proceeds in a transition-metal-, acid-, base- and external oxidant-free fashion to provide a variety of functionalized 1,2,4-triazoles. The reaction constitutes a new transformation from hydrazones and amines to 1,2,4-triazoles, providing a unifying, simple and environmentally friendly approach to the currently available methods.

Key words: 1,2,4-triazoles, [3+2] annulation, electrochemical synthesis, green chemistry.

Cite this article

Zhiheng Zhao, Ming Li, Yaqin Zhou, Yonghui He, Lizhu Zhang, Ganpeng Li, Lijun Gu. Synthesis of 1,2,4-Triazoles via the Electrochemical Oxidative [3+2] Annulation[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2476-2484.

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Fig. & Tab. 7

Figure 1. Different methods for the synthesis of substituted 1,2,4-triazoles

Scheme 1. Electrochemical dehydrogenative [3+2] annulation used for the synthesis of target compounds

Entry	Variation from the standard conditions	Yield^b/%
1	None	85
2	1 h instead of 2 h	62
3	NaI instead of TBAI	72
4	HI instead of TBAI	69
5	NH₄I instead of TBAI	74
6	ⁿBu₄NBr instead of TBAI	57
7	Pt(+)\|Pt(–) instead of C(+)\|C(–)	13
8	Pt(+)\|C(–) instead of C(+)\|C(–)	15
9	12 mA instead of 15 mA	75
10	18 mA instead of 15 mA	68
11	DMSO instead of MeCN	28
12	DMF instead of MeCN	39
13	DCM instead of MeCN	30
14	EtOH instead of MeCN	trace
15	ⁿBu₄NBF₄instead of LiClO₄	71
16	ⁿBu₄NPF₆instead of LiClO₄	70
17	60 ℃instead of room temperature	72
18	Air instead of Ar	78
19	No current	n.d.
20	Without TBAI	n.d.
21^c	Large-scale reaction	75

Table 1. Optimization of reaction conditions for the synthesis of 3aa

Table 2. Scope of hydrazones 1 used in the reaction

Table 3. Scope of amines 2 used in the reactiona

Figure 2. Cyclic voltammograms of 0.1 mol/L of LiClO4 in acetonitrile (10 mL) solution containing different compounds (a) Blank experiment; (b) only benzyl amine (0.045 mol/L); (c) only 1-benzylidene-2-phenylhydrazine (0.03 mol/L); (d) only tetrabutylammonium iodide (0.006 mol/L); (e)1-benzylidene-2-phenylhydrazine (0.03 mol/L), tetrabutylammonium iodide (0.006 mol/L); (f) benzyl amine (0.045 mol/L), tetrabutylammonium iodide (0.006 mol/L) (g) 1-benzylidene-2-phenylhydrazine (0.03 mol/L), benzyl amine (0.045 mol/L), tetrabutylammonium iodide (0.006 mol/L); with a GC disk working electrode, Pt counter electrode, and SCE reference electrode at 0.01 V/s scan rate

Scheme 2. Possible reaction mechanism

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电化学脱氢[3+2]环化反应合成取代的1,2,4-三氮唑衍生物

Synthesis of 1,2,4-Triazoles via the Electrochemical Oxidative [3+2] Annulation

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