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
收稿日期: 2022-09-17
修回日期: 2022-12-06
网络出版日期: 2022-12-14
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
Received date: 2022-09-17
Revised date: 2022-12-06
Online published: 2022-12-14
Supported by
National Natural Science Foundation of China(22071058)
1,2,3-三氮唑N1、N3原子电子云比N2原子电子云更加富集, 更容易发生各类化学转化, 因此其研究更为充分. 相较而言, 高区域选择性合成N2-1,2,3-三氮唑的研究相对有限. 采用天然来源且价廉易得的醇替代卤代试剂, 与N-磺酰基-1,2,3-三氮唑偶联, 在无需添加任何催化剂或添加剂条件下, 通过原位生成的磺酸催化, 高区域选择性、高收率(68%~83%)地合成了N2-取代1,2,3-三氮唑. 该反应具有广阔的底物适应性, 芳基苄醇和烷基醇等都具有良好的官能团兼容性. 初步机理研究显示, N-磺酰基-1,2,3-三氮唑水解产生的甲基磺酸有效催化了反应中的亲核取代过程, 并通过热稳定中间体N2H-1,2,3-三氮唑实现了高区域选择性.
关键词： 高区域选择性; 无金属催化; N2-取代1,2,3-三氮唑; 绿色合成
纪健 , 刘进华 , 管丛 , 陈绪文 , 赵芸 , 刘顺英 . 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[J]. 有机化学, 2023 , 43(3) : 1168 -1176 . DOI: 10.6023/cjoc202209021
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.
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