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

Sebastian Lips; Robert Franke; Siegfried R. Waldvogel

doi:10.1055/s-0037-1611942

Synlett, Table of Contents

Synlett 2019; 30(10): 1174-1177
DOI: 10.1055/s-0037-1611942

cluster

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

Sebastian Lips

^aJohannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

,

Robert Franke

^bEvonik Performance Materials GmbH, Paul-Baumann-Straße 1, 45772 Marl, Germany

^cLehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany

,

Siegfried R. Waldvogel *

^aJohannes Gutenberg University Mainz, Institute of Organic Chemistry, Duesbergweg 10-14, 55128 Mainz, Germany Email: waldvogel@uni-mainz.de

› Author Affiliations

Abstract

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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

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References

References and Notes

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32 Introduction of Protecting Group (4, AB^PG) 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.
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34 Synthesis of Teraryl (5a, AB^PGA′); 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 (AB^PG ) (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.
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