High Regioselective Synthesis of N2-Substituted-1,2,3-triazole via N-Sulfonyl-1,2,3-triazole Coupling with Alcohol Catalyzed by in-situ Generated Sulfonic Acid

doi:10.6023/cjoc202209021

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (3): 1168-1176.DOI: 10.6023/cjoc202209021 Previous Articles Next Articles

Special Issue: 中国女科学家专辑

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原位生成的磺酸催化N-磺酰基-1,2,3-三氮唑与醇偶联高区域选择性合成N²-取代1,2,3-三氮唑

纪健, 刘进华, 管丛, 陈绪文, 赵芸, 刘顺英^*()

华东师范大学化学与分子工程学院上海 200062

收稿日期:2022-09-17 修回日期:2022-12-06 发布日期:2022-12-14
通讯作者: 刘顺英
基金资助:
国家自然科学基金(22071058)

High Regioselective Synthesis of N²-Substituted-1,2,3-triazole via N-Sulfonyl-1,2,3-triazole Coupling with Alcohol Catalyzed by in-situ Generated Sulfonic Acid

Jian Ji, Jinhua Liu, Cong Guan, Xuwen Chen, Yun Zhao, Shunying Liu()

School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062

Received:2022-09-17 Revised:2022-12-06 Published:2022-12-14
Contact: Shunying Liu
Supported by:
National Natural Science Foundation of China(22071058)

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Abstract

The green and highly efficient synthesis of N²-substituted 1,2,3-triazoles remains challenging due to the lower electron density at the N²-atom than that at two terminal nitrogen atoms (N¹ and N³) of the triazole heterocycle. Cheap and easily available alcohols were developed as starting points to couple with N-sulfonyl-1,2,3-triazole instead of halogenated reagents catalyzed by in-situ generated sulfonic acid. The resulting products, N²-substituted 1,2,3-triazoles, were obtained with high regioselectivity and in good yields (68%~83%) without any additional catalysts or additives. The reaction has a broad substrate adaptability and functional group compatibility, including aryl benzyl and alkyl alcohols. Preliminary mechanistic studies indicate that methanesulfonic acid (MsOH) which in situ produced by the hydrolysis of N-sulfonyl-1,2,3-triazoles promoted the reaction, and high regioselectivity was promoted through the thermally stable intermediate N²H-1,2,3-triazole.

Key words: high regioselectivity, free-catalysis, N²-substituted 1,2,3-triazole, green synthesis

Cite this article

Jian Ji, Jinhua Liu, Cong Guan, Xuwen Chen, Yun Zhao, Shunying Liu. High Regioselective Synthesis of N²-Substituted-1,2,3-triazole via N-Sulfonyl-1,2,3-triazole Coupling with Alcohol Catalyzed by in-situ Generated Sulfonic Acid[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1168-1176.

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Entry	Additive	Solvent	Temp./℃	Yield^b/%
Entry	Additive	Solvent	Temp./℃	3a	3a'
1	TsOH	DCE	rt	n.d.	n.d.
2	TsOH	DCE	50	n.d.	n.d.
3	TsOH	DCE	80	n.d.	n.d.
4	TsOH	DCE	100	50	5
5	TsOH	DCE	120	80	8
6	TsOH	DCE	130	76	10
7^c	TsOH	DCE	120	80	10
8	None	DCE	120	82	12
9	None	PhMe	120	72	8
10	None	CH₃CN	120	63	10
11	None	DMF	120	45	5
12	None	DMSO	120	55	7
13^d	None	DCE	120	82	12
14^e	None	DCE	120	52	6
15	None	DCE	120	45	5

Entry	Additive	Solvent	Temp./℃	Yield^b/%
Entry	Additive	Solvent	Temp./℃	3a	3a'
1	TsOH	DCE	rt	n.d.	n.d.
2	TsOH	DCE	50	n.d.	n.d.
3	TsOH	DCE	80	n.d.	n.d.
4	TsOH	DCE	100	50	5
5	TsOH	DCE	120	80	8
6	TsOH	DCE	130	76	10
7^c	TsOH	DCE	120	80	10
8	None	DCE	120	82	12
9	None	PhMe	120	72	8
10	None	CH₃CN	120	63	10
11	None	DMF	120	45	5
12	None	DMSO	120	55	7
13^d	None	DCE	120	82	12
14^e	None	DCE	120	52	6
15	None	DCE	120	45	5

原位生成的磺酸催化N-磺酰基-1,2,3-三氮唑与醇偶联高区域选择性合成N²-取代1,2,3-三氮唑

High Regioselective Synthesis of N²-Substituted-1,2,3-triazole via N-Sulfonyl-1,2,3-triazole Coupling with Alcohol Catalyzed by in-situ Generated Sulfonic Acid

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