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Synlett 2017; 28(15): 1990-1993
DOI: 10.1055/s-0036-1589059
letter
© Georg Thieme Verlag Stuttgart · New York

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

Ana-Luiza Lücke
Clausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany   eMail: schmidt@ioc.tu-clausthal.de
,
Sascha Wiechmann
Clausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany   eMail: schmidt@ioc.tu-clausthal.de
,
Tyll Freese
Clausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany   eMail: schmidt@ioc.tu-clausthal.de
,
Andreas Schmidt*
Clausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany   eMail: schmidt@ioc.tu-clausthal.de
› InstitutsangabenThe Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged for financial support
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Publikationsverlauf

Received: 31. März 2017

Accepted after revision: 20. Mai 2017

Publikationsdatum:
29. Juni 2017 (online)

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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

Supporting Information

    Supporting information for this article is available online at https://doi.org /10.1055/s-0036-1589059.
  • Supporting Information
 

  • 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.