Suzuki–Miyaura Cross-Coupling Reactions in Acetic Acid Employing Sydnone-Derived Catalyst Systems

Abstract

The catalyst system consisting of lithium N-phenylsydnone-4-carboxylate/Pd(PPh₃)₄ has proven to be an effective catalyst for the Suzuki–Miyaura reaction of 2,4-dinitrochlorobenzene with boronic acids in acetic acid at pH 5.7, whereas the N-phenylsydnone carbene palladium complex [sydPd(PPh₃)₂Br] required pH 8.0.

Key words

catalysis - Suzuki–Miyaura reaction - N-heterocyclic carbenes - sydnones - palladium - pH value

• References and Notes

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• 16 General Procedure for the Preparation of Compounds 7a–h Under a nitrogen atmosphere samples of 1-chloro-2,4-dinitrobenzene (1, 0.050 g, 0.2 mmol) were dissolved in anhydrous 1,4-dioxane (8 mL) and treated with the catalyst (cat. 1–6, 10 mol%). The mixtures were subjected to ultrasound irradiation for 5 min and then stirred at r.t. for additional 25 min. Then, the corresponding boronic acid 6a–h (2 equiv), sodium carbonate (4.7 mmol), and water (2 mL) were added. The mixtures were heated at 70 °C for 30 min. After cooling to r.t. the mixtures were dried over MgSO₄. The resulting crude products were purified by column chromatography over silica gel (40–60 mesh) using a PE-CH₂Cl₂ (1:3) mixture as eluent. The analytical data and the characterization of each produced compound can be found in the Supporting Information. 2,4-Dinitro-1,1′:4′,1′′-terphenyl (7f) A sample of 1-(4-biphenyl)-boronic acid (0.098 g, 0.5 mmol), cat. 1 (10 mol%), Na₂CO₃ (4.7 mmol), and AcOH (17 mmol) were used. The reaction was monitored by TLC. The product was isolated as a yellowish solid; yield 91%; mp 154 °C. ¹H NMR (600 MHz, CDCl₃): δ = 7.41–7.42 (m, 3 H, H-2′, H-4′, H-6′), 7.47–7.49 (m, 2 H, H-3′′, H-5′′), 7.62–7.64 (d, J = 7.7 Hz, 2 H, H-2′′, H-6′′), 7.69–7.72 (m, 3 H, H-3′, H-5′, H-6′), 8.46–8.48 (dd, J = 7.7 Hz, 1 H, H-5), 8.72 (s, 1 H, H-3) ppm. ¹³C NMR (150 MHz, CDCl₃): δ = 119.7 (+, 1 C, C-3), 126.5 (+, 1 C, C-5), 127.1 (+, 2 C, C-6′′, C-2′′), 127.7 (+, 2 C, C-3′, C-5′), 128.0 (+, 1 C, C-4′′), 128.1 (+, 2 C, C-6′, C-2′), 128.9 (+, 2 C, C-3′′, C-5′′), 133.1 (+, 1 C, C-6), 133.9 (o, 1 C, C-1′), 139.7 (o, 1 C, C-1′′), 141.8 (o, 1 C, C-1), 142.4 (o, 1 C, C-4′), 146.8 (o, 1 C, C-4), 149.0 (o, 1 C, C-2) ppm. IR (ATR): ν = 666, 833, 1274, 1489, 1598, 3079 cm^–1. MS (EI-MS, 70 eV): m/z (C₁₈H₁₂N₂O₄) = 320.1. HRMS (EI, 70 eV): m/z calcd for [C₁₈H₁₂N₂O₄]⁺: 320.0797; found: 320.0797.