Synlett 2019; 30(10): 1174-1177
DOI: 10.1055/s-0037-1611942
cluster
© Georg Thieme Verlag Stuttgart · New York

Electrochemical Synthesis of 2-Hydroxy-para-terphenyls by Dehydrogenative Anodic C–C Cross-Coupling Reaction

Sebastian Lips
a   Johannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany   Email: waldvogel@uni-mainz.de
,
Robert Franke
b   Evonik Performance Materials GmbH, Paul-Baumann-Straße 1, 45772 Marl, Germany
c   Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany
,
Siegfried R. Waldvogel  *
a   Johannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany   Email: waldvogel@uni-mainz.de
› Author AffiliationsS.R.W. thanks the DFG (Wa1276/14-1) for financial support. S.L. and S.R.W. acknowledge the Carl-Zeiss Foundation for granting a fellowship and the research network ELYSION, respectively.
Further Information

Publication History

Received: 14 November 2018

Accepted after revision: 04 December 2018

Publication Date:
08 January 2019 (online)

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Published as part of the Cluster Electrochemical Synthesis and Catalysis

Abstract

The anodic C–C cross-coupling reaction provides fast access to a wide range of bi- and terarylic scaffolds by electrochemically mediated arylation reactions. Herein, a metal- and reagent-free electrosynthetic protocol for the synthesis of nonsymmetrical 2-hydroxy-para-teraryl derivatives is presented for the first time. It is scalable, easy to conduct, and allows the use of a broad variety of different functional groups.

Key words

C–C coupling - protecting groups - electrochemistry - C–H activation - arylation - terphenyls

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611942.
  • Supporting Information
 

  • References and Notes

  • 3 von Nussbaum F, Brands M, Hinzen B, Weigand S, Häbich D. Angew. Chem. Int. Ed. 2006; 45: 5072 ; Angew. Chem. 2006, 118, 5194
    CrossrefPubMedSearch in Google Scholar
  • 4 Shukla R, Lindeman SV, Rathore R. Chem. Commun. 2009; 5600
    PubMed
    • 5a Albrecht M, Schneider M. Eur. J. Inorg. Chem. 2002; 1301
    • 5b Albrecht M, Schneider M. Synthesis 2000; 1557
      Thieme Connect
  • 6 Peters M, Trobe M, Tan H, Kleineweischede R, Breinbauer R. Chem. Eur. J. 2013; 19: 2442
    CrossrefPubMedSearch in Google Scholar
  • 7 Koch F, Berkefeld A, Schubert H, Grauer C. Chem. Eur. J. 2016; 22: 14640
    CrossrefPubMedSearch in Google Scholar
  • 8 Koch F, Schubert H, Sirsch P, Berkefeld A. Dalton Trans. 2015; 13315
    PubMed
  • 9 Buss JA, Edouard GA, Cheng C, Shi J, Agapie T. J. Am. Chem. Soc. 2014; 136: 11272
    CrossrefPubMedSearch in Google Scholar
  • 11 Huguet N, Lebœuf D, Echavarren AM. Chem. Eur. J. 2013; 19: 6581
    CrossrefPubMedSearch in Google Scholar
  • 13 Waldvogel SR, Lips S, Selt M, Riehl B, Kampf CJ. Chem. Rev. 2018; 118: 6706
    CrossrefPubMedSearch in Google Scholar
  • 17 Elsler B, Wiebe A, Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Chem. Eur. J. 2015; 21: 12321
    CrossrefPubMedSearch in Google Scholar
  • 18 Schulz L, Enders M, Elsler B, Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Angew. Chem. Int. Ed. 2017; 56: 4877 ; Angew. Chem. 2017, 129, 4955
    CrossrefPubMedSearch in Google Scholar
  • 19 Wiebe A, Lips S, Schollmeyer D, Franke R, Waldvogel SR. Angew. Chem. Int. Ed. 2017; 56: 14727 ; Angew. Chem. 2017, 129, 14920
    CrossrefPubMedSearch in Google Scholar
  • 20 Dahms B, Franke R, Waldvogel SR. ChemElectroChem 2018; 5: 1249
    CrossrefSearch in Google Scholar
  • 21 Lips S, Frontana-Uribe BA, Dörr M, Schollmeyer D, Franke R, Waldvogel SR. Chem. Eur. J. 2018; 24: 6057
    CrossrefPubMedSearch in Google Scholar
  • 22 Lips S, Schollmeyer D, Franke R, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 13325 ; Angew. Chem. 2018, 130, 13509
    CrossrefPubMedSearch in Google Scholar
  • 23 Lips S, Wiebe A, Elsler B, Schollmeyer D, Dyballa KM, Franke R, Waldvogel SR. Angew. Chem. Int. Ed. 2016; 55: 10872 ; Angew. Chem. 2016, 128, 11031
    CrossrefPubMedSearch in Google Scholar
  • 24 Organic Electrochemistry . Speiser B, Hammerich O. CRC Press Taylor & Francis Group; Boca Raton: 2016
    Search in Google Scholar
  • 25 Horn EJ, Rosen BR, Baran PS. ACS Cent. Sci. 2016; 2: 302
    CrossrefPubMedSearch in Google Scholar
  • 27 Wiebe A, Riehl B, Lips S, Franke R, Waldvogel SR. Sci. Adv. 2017; 3: eaao3920
    CrossrefPubMedSearch in Google Scholar
  • 28 Hollóczki O, Berkessel A, Mars J, Mezger M, Wiebe A, Waldvogel SR, Kirchner B. ACS Catal. 2017; 7: 1846
    CrossrefSearch in Google Scholar
  • 29 Colomer I, Chamberlain AE. R, Haughey MB, Donohoe TJ. Nat. Rev. Chem. 2017; 1: 88
    CrossrefSearch in Google Scholar
  • 30 Synthesis of Phenol Arene (3, AB); General Procedure 1,4-Dimethoxybenzene (0.69 g, 5.00 mmol, 1.0 equiv), 4-(1,1-dimethylethyl)-2-methylphenol (1.64 g, 10.0 mmol, 2.0 equiv) and MTBS (0.70 g, 0.09 M) were dissolved in HFIP (25 mL) and transferred to the electrolysis cell. After electrolysis, the solvent was recovered by distillation. Short-path distillation of the residue yielded the desired product as a yellow oil.
    • 31a Sala T, Sargent MV. J. Chem. Soc., Perkin Trans. 1 1979; 2593
      Crossref
    • 31b Greene TW, Wuts PG. M. Greene’s Protective Groups in Organic Synthesis . Wiley-Interscience; Hoboken, NJ: 2007
      Search in Google Scholar
  • 32 Introduction of Protecting Group (4, ABPG) 2-Hydroxy-5-methyl-2′,3,4′-trimethoxybiphenyl (4.00 g, 13.3 mmol, 1.0 equiv) was dissolved in anhydrous DMF in a 250 mL round-bottom flask. Sodium hydride (60% dispersion, 0.72 g, 17.29 mmol, 1.3 equiv) was added under nitrogen atmosphere. After 1 hour stirring at room temperature, 2-bromopropane (3.27 g, 26.6 mmol, 2.0 equiv) was added. The reaction mixture was stirred for 3 h at room temperature. The crude product was purified as described in Ref. 34.
  • 33 Gütz C, Klöckner B, Waldvogel SR. Org. Process Res. Dev. 2015; 20: 26
    Search in Google Scholar
  • 34 Synthesis of Teraryl (5a, ABPGA′); General Procedure 2,4-Dimethylphenol (A′) (0.61 g, 5.00 mmol, 1.0 equiv), 2′,5′-dimethoxy-2-(1-methylethoxy)-3-methyl-5-(1,1-dimethylethyl)biphenyl (ABPG ) (4.28 g, 12.5 mmol, 2.5 equiv) and MTBS (0.70 g) were dissolved in HFIP (25 mL) and transferred into a beaker type cell. Electrolysis was carried out at room temperature with a current density of 5.2 mA/cm². After electrolysis (2.5 F per A′), the solvent was recovered by distillation. Column chromatography of the residue (cyclohexane/ethyl acetate = 99:0.5 → 99:1 → 95:5 → 90:10, total solvent volume: 5 L; column 40 mm × 150 mm) gave the product 5a (1.09 g, 2.36 mmol, 47%) as a yellow oil. 1H NMR (400 MHz, CDCl3): δ = 1.02 (s, 3 H), 1.03 (s, 3 H), 1.37 (s, 9 H), 2.36 (s, 6 H), 2.37 (s, 3 H), 3.78 (sep, 1 H), 3.82 (s, 3 H), 3.88 (s, 3 H), 6.47 (br s, 1 H), 6.99 (s, 1 H), 7.04 (d, J = 6.0 Hz, 2 H), 7.14 (s, 1 H), 7.22–7.25 (m, 2 H); 13C NMR (101 MHz, CDCl3): δ = 16.55, 17.47, 20.63, 22.56, 31.58, 34.23, 56.48, 57.06, 75.35, 115.70, 115.93, 125.81, 126.41, 126.84, 126.94, 127.46, 128.98, 129.45, 129.67, 130.28, 131.06, 131.45, 145.01, 148.88, 149.70, 151.76, 151.94. HRMS (ESI+): m/z [M+Na+] calcd. for C30H38O4: 485.2657; found: 485.2678.
  • 35 Banwell MG, Flynn BL, Stewart SG. J. Org. Chem. 1998; 63: 9139
    CrossrefSearch in Google Scholar