Tandem Oxidative Reaction of 1,3-Diarylpropenes and 5-Aminopyrazoles

Abstract

The reaction of 5-aminopyrazoles with 1,3-diarylpropenes mediated by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, with subsequent intramolecular cyclization and dehydroaromatization in the presence of Cu(OTf)₂/tert-butyl hydroperoxide, gave a series of pyrazolo[3,4-b]pyridines in moderate to excellent yields. The reaction has the advantages of high atom economy, a wide substrate scope, and a one-pot procedure.

Key words

oxidative coupling - tandem reaction - one-pot reaction - aminopyrazoles - diarylpropenes - pyrazolopyridines

Publication History

Received: 30 May 2023

Accepted after revision: 31 July 2023

Accepted Manuscript online:
31 July 2023

Article published online:
14 September 2023

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• 14 Pyrazolo[3,4-b]pyridines 3a–gg; General Procedure DDQ (0.12 mmol, 1.2 equiv) was added to a solution of the appropriate 1,3-diarylpropene 2 (0.12 mmol, 1.2 equiv) in 1,4-dioxane (3 mL), and the mixture was stirred for 10 min. The appropriate 5-aminopyrazole 1 (0.10 mmol, 1.0 equiv) was then added, and the mixture was stirred at r.t. for 2 h. Cu(OTf)₂ (0.02 mmol, 0.2 equiv) and a solution of TBHP (0.2 mmol, 2.0 equiv) in decane (0.02 mL) were added, and the resultant mixture was stirred at 80 °C (oil bath) for 1 h. When the reaction was complete, the solvent was evaporated under reduced pressure, and the residue was purified by column chromatography [silica gel (200–300 mesh), PE–EtOAc (10:1–60:1)]. 1,3,4,6-Tetraphenyl-1H-pyrazolo[3,4-b]pyridine (3a) ¹⁵ Light-yellow solid; yield: 33.8 mg (80%). ¹H NMR (400 MHz, CDCl₃): δ = 8.63–8.60 (m, 2 H), 8.33–8.30 (m, 2 H), 7.79 (s, 1 H), 7.68–7.53 (m, 5 H), 7.44–7.25 (m, 9 H), 7.22–7.18 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 156.71, 152.02, 146.64, 145.90, 139.79, 139.11, 137.48, 133.00, 129.60, 129.36, 129.26, 129.02, 128.89, 128.42, 128.03, 127.82, 127.68, 127.63, 125.85, 121.56, 116.07, 112.20. HRMS (ESI): m/z [M + H]⁺ calcd for C₃₀H₂₂N₃: 424.1808; found: 424.1808.
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