Synthesis of (E)-4,5-Dihydro-1H-Pyrazoles via Tandem Intermolecular Addition–Cyclization of N-Propargylic Sulfonylhydrazones

Hai-Tao Tang; Jia-Hao Zeng; Jun-Jia Chen; Yi-Hui Chen; Zhuang-Ping Zhan

doi:10.1055/s-0036-1588844

Synlett, Table of Contents

Synlett 2017; 28(15): 2036-2040
DOI: 10.1055/s-0036-1588844

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Synthesis of (E)-4,5-Dihydro-1H-Pyrazoles via Tandem Intermolecular Addition–Cyclization of N-Propargylic Sulfonylhydrazones

Hai-Tao Tang

Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, P. R. of China Email: yhchen@xmu.edu.cn

,

Jia-Hao Zeng

Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, P. R. of China Email: yhchen@xmu.edu.cn

,

Jun-Jia Chen

Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, P. R. of China Email: yhchen@xmu.edu.cn

,

Yi-Hui Chen*

Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, P. R. of China Email: yhchen@xmu.edu.cn

,

Zhuang-Ping Zhan

Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, P. R. of China Email: yhchen@xmu.edu.cn

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Abstract

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Abstract

A new strategy for the synthesis of (E)-4-benzylidene-4,5-dihydro-1H-pyrazoles through tandem intermolecular addition–intramolecular cyclization of N-propargylic sulfonylhydrazones has been developed. In this study, we firstly report that N-propargylic sulfonylhydrazones react with electrophilic reagents to afford 4-substituted pyrazole derivatives.

Key words

propargyl hydrazones - dihydropyrazoles - acetals - intermolecular reaction

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References

References and Notes

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13 CCDC 1540257 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
14 Representative Procedure for the Preparation of (E)-4-Benzylidene-4,5-dihydro-1H-pyrazoles 2 To a solution of N-propargylic sulfonylhydrazone 1 (0.5 mmol) and acetals 3 (1 mmol) in DBE (5 mL), FeCl₃ (0.1 mmol) was added, and the mixture was stirred at 80 °C. When the reaction was completed (monitored by TLC), water was added to the mixture. The aqueous phase was extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layers were washed with brine and dried over Na₂SO₄. The solvent was removed under vacuum, and then the residue was further purified by silica gel column chromatography (PE and EtOAc) to afford product 2.
15 Representative Analytical Data of (E)-4-Benzylidene-3-phenyl-1-tosyl-4,5-dihydro-1H-pyrazole (2a) White solid (mp 149–150 °C). ¹H NMR (500 MHz, CDCl₃): δ = 2.43 (s, 3 H), 4.81 (s, 2 H), 6.74–6.80 (m, 1 H), 7.25 (d, 2 H, J = 7.3 Hz), 7.32–7.38 (m, 3 H), 7.41–7.52 (m, 5 H), 7.60 (d, 2 H, J = 7.1 Hz), 7.88(d, 2 H, J = 8.0 Hz). ¹³C NMR (125 MHz, CDCl₃): δ = 21.6, 54.2, 126.3, 128.6, 128.7, 128.8, 128.8, 128.9, 129.7, 129.8, 130.1, 132.0, 133.9, 135.3, 144.5, 160.1. ESI-HRMS: m/z calcd for C₂₃H₂₀N₂O₂S [M + H]⁺: 389.1318; found: 389.1322.

Supplementary Material

Supporting Information