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Synlett 2021; 32(03): 316-320
DOI: 10.1055/s-0040-1707262
DOI: 10.1055/s-0040-1707262
letter
Palladium-Catalyzed Synthesis of Polysubstituted Pyrazoles by Ring-Opening Reactions of 2H-Azirines with Hydrazones
This research was supported by the Zhejiang Provincial Natural Science Foundation of China under Grant No. LY20H300001, the Medical Health Science and Technology Project of Zhejiang Provincial Health Commission under Grant No. 2020KY681, and The Second Round of ‘West Lake Scholar’ Introduction Plan of Hangzhou Municipal University in 2019 for J.S.; Zhejiang Provincial Natural Science Foundation of China under Grant No. LY18H300001 for W.C.; and The Second Round of Excellent Innovation Team of Hangzhou Municipal University in 2019 for L.-H.Z.
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Abstract
A palladium–catalyzed ring-opening reaction of 2H-azirines with hydrazones has been developed. This protocol provides an alternative route for the construction of various polysubstituted pyrazoles with a wide substrate scope. Moreover, a plausible mechanism is proposed for this reaction, which should further enrich the chemical conversion of 2H-azirines.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707262.
- Supporting Information
Publication History
Received: 21 June 2020
Accepted after revision: 28 July 2020
Article published online:
28 August 2020
© 2020. Thieme. All rights reserved
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17
Polysubstituted Pyrazoles 3a–t; General ProcedureThe appropriate 2H-azirine (1; 1.05 mmol), hydrazone 2 (1.0 mmol), Pd(OAc)2 (10 mol%), K2S2O8 (2.0 mmol), CsF (1.0 mmol), and anhyd 1,4-dioxane (6 mL) were sequentially added to a sealed tube under N2, and the mixture was stirred at 100 °C for about 12 h until the reaction was complete (TLC). The mixture was then filtered through diatomite, and the filter cake was washed with EtOAc(10 mL). The filtrate was collected and concentrated under reduced pressure, and the crude product was purified by chromatography [silica gel, PE–EtOAc (40:1)].3-(4-Bromophenyl)-1,4-diphenyl-1H-pyrazole
(3a)Yellow solid; yield: 281 mg (75%); mp 113.4–114.7 °C. 1H NMR (500 MHz, DMSO-d
6): δ = 8.78 (s, 1 H), 7.95 (d, J = 7.8 Hz, 2 H), 7.59 (d, J = 8.5 Hz, 2 H), 7.54 (t, J = 7.9 Hz, 2 H), 7.45 (d, J = 8.5 Hz, 2 H), 7.41–7.31 (m, 6 H). 13C NMR (125 MHz, DMSO-d
6): δ = 148.2, 139.3, 132.2, 132.1, 131.4, 129.9, 129.5, 128.6, 128.3, 128.3, 127.1, 126.5, 122.2, 121.3, 118.4. HRMS (ESI): m/z [M+ H]+ calcd for C21H16BrN2: 375.0491; found: 375.0492.
For reviews on 2H-azirine chemistry, see: