Citation: 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]. Chinese Journal of Organic Chemistry, ;2019, 39(6): 1630-1641. doi: 10.6023/cjoc201903046 shu

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

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

Corresponding author: Fan Xuesen, xuesen.fan@htu.cn
Received Date: 23 March 2019
Revised Date: 14 May 2019
Available Online: 21 June 2019
Fund Project: the Plan for Scientific Innovation Talents of Henan Province 184200510012Project supported by the National Natural Science Foundation of China (No. 21572047) and the Plan for Scientific Innovation Talents of Henan Province (No. 184200510012)the National Natural Science Foundation of China 21572047

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