由饱和酮与肼/醛腙的[3+2]/[2+3]环化反应区域选择性合成多取代吡唑

doi:10.6023/cjoc201903046

有机化学 ›› 2019, Vol. 39 ›› Issue (6): 1630-1641.DOI: 10.6023/cjoc201903046 上一篇下一篇

所属专题：金属有机化学

研究论文

由饱和酮与肼/醛腙的[3+2]/[2+3]环化反应区域选择性合成多取代吡唑

师晓楠, 田苗苗, 王慕华, 张新迎, 范学森

河南师范大学化学化工学院河南省有机功能分子与药物创新重点实验室绿色化学介质与反应教育部重点实验室新乡 453007

收稿日期:2019-03-23 修回日期:2019-05-14 发布日期:2019-05-21
通讯作者: 范学森 E-mail:xuesen.fan@htu.cn
基金资助:
国家自然科学基金（No.21572047）和河南省科技创新杰出人才（No.184200510012）资助项目.

Regioselective Synthesis of Substituted Pyrazoles via[3+2]/[2+3] Cyclization of Saturated Ketone with Hydrazine/Aldehyde Hydrazone

Shi Xiaonan, Tian Miaomiao, Wang Muhua, Zhang Xinying, Fan Xuesen

Henan Key Laboratory of Organic Functional Molecules and Drug Innovation, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007

Received:2019-03-23 Revised:2019-05-14 Published:2019-05-21
Contact: 10.6023/cjoc201903046 E-mail:xuesen.fan@htu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21572047) and the Plan for Scientific Innovation Talents of Henan Province (No. 184200510012).

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摘要/Abstract

报道了一种经由二价铜催化饱和酮与肼或醛腙的串联反应合成1，3-二取代吡唑或1，3，4-三取代吡唑类化合物的简便和区域选择性新方法.从机理上看，1，3-二取代吡唑的生成经历了烯酮中间体的原位生成及其与肼的[3+2]环化反应，而1，3，4-三取代吡唑的生成则经历了烯酮中间体的原位生成及其与醛腙的[2+3]环化反应.与文献方法相比，该方法具有原料简单易得、底物适用范围广、区域选择性好、效率高、原子经济性优异等优势.

关键词: 吡唑合成, 二价铜催化反应, C(sp³)-H官能团化, [3+2]环化, [2+3]环化

A highly convenient and regioselective synthesis of 1,3-disubstituted pyrazoles or 1,3,4-trisubstituted pyrazoles from Cu(Ⅱ)-catalyzed cascade reactions of saturated ketones with hydrazines or aldehyde hydrazones is presented. Mechanistically, the formation of 1,3-disubstituted pyrazoles involves the in situ generation of an enone intermediate followed by its[3+2] annulations with hydrazine. On the other hand, the formation of 1,3,4-trisubstituted pyrazoles is believed to go through a cascade process including enone formation and its subsequent[2+3] annulation with aldehyde hydrazone. Compared with literature methods, the notable features of the protocol include simple starting materials, general and broad substrate scope, high regioselectivity, good efficiency and excellent atom-economy.

Key words: pyrazole synthesis, Cu(Ⅱ) catalyzed reaction, C(sp³)-H functionalization, [3+2] annulation, [2+3] annulation

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师晓楠, 田苗苗, 王慕华, 张新迎, 范学森. 由饱和酮与肼/醛腙的[3+2]/[2+3]环化反应区域选择性合成多取代吡唑[J]. 有机化学, 2019, 39(6): 1630-1641.

Shi Xiaonan, Tian Miaomiao, Wang Muhua, Zhang Xinying, Fan Xuesen. Regioselective Synthesis of Substituted Pyrazoles via[3+2]/[2+3] Cyclization of Saturated Ketone with Hydrazine/Aldehyde Hydrazone[J]. Chin. J. Org. Chem., 2019, 39(6): 1630-1641.

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由饱和酮与肼/醛腙的[3+2]/[2+3]环化反应区域选择性合成多取代吡唑

Regioselective Synthesis of Substituted Pyrazoles via[3+2]/[2+3] Cyclization of Saturated Ketone with Hydrazine/Aldehyde Hydrazone

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