Citation: Wang Xucai, Chen Ming, Zhang Wei, Zhang Yaodu, Ren Zhihui, Guan Zhenghui. Palladium-Catalyzed 5-exo-trig Hydroamidation of β, γ-Unsaturated Hydrazones for Synthesis of Dihydropyrazoles[J]. Chinese Journal of Organic Chemistry, ;2020, 40(6): 1618-1624. doi: 10.6023/cjoc202002009 shu

Palladium-Catalyzed 5-exo-trig Hydroamidation of β, γ-Unsaturated Hydrazones for Synthesis of Dihydropyrazoles

Key Laboratory of Synthetic and Nature Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi'an 710127

Corresponding author: Guan Zhenghui, guanzhh@nwu.edu.cn

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Received Date: 8 February 2020
Revised Date: 23 March 2020
Available Online: 31 March 2020
Fund Project: the Innovation Capability Support Program of Shaanxi Province 2020TD-022the National Natural Science Foundation of China 216222203Project supported by the National Natural Science Foundation of China (Nos. 21971204, 216222203, 21702161), the Innovation Capability Support Program of Shaanxi Province (No. 2020TD-022), and the Education Department of Shaanxi Province (No. 19JS064)the National Natural Science Foundation of China 21702161the National Natural Science Foundation of China 21971204the Education Department of Shaanxi Province 19JS064

Figures(5)

Hydroamination reaction is the addition of a N-H unit across the unsaturated C-C bond, which provides a convenient route for the formation of C-N bond. Considerable effort has been directed toward the development of multiple catalytic protocols for the hydroamination reaction in the past decades. Despite appreciable progress in this field, the development of general and practical strategy for the hydroamination of amides remains challenging, because the strong electron-with-drawing substituents (acyl, sulfonyl, or phosphinyl) strongly declined the nucleophilicity of the nitrogen. In this paper, a mild and efficient palladium-catalyzed 5-exo-trig hydroamidation of β, γ-unsaturated hydrazones for the synthesis of dihydropyrazoles has been developed. The reaction employs readily available starting materials, tolerates a wide range of functional groups, and produces a series of valuable dihydropyrazoles in good to high yields (63%~88%) under mild reaction conditions. Furthermore, a gram-scale hydroamidation of 1a afforded the dihydropyrazole 2a in 85% yield. In addition, the deuterium labeling experiment demonstrated that N-H is the hydrogen source in this hydroamidation process.
- palladium-catalyzed,
- hydroamidation,
- unsaturated hydrazones,
- dihydropyrazole,
- N-heterocycles
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