Dimerization of Aromatic Compounds Using Palladium-Carbon-Catalyzed Suzuki–Miyaura Cross-Coupling by One-Pot Synthesis

Abstract

The aromatic dimers play a significant role in many aspects. Herein, we report a simple palladium-carbon catalyst that is highly effective for the dimerization of brominated aromatic compounds under mild conditions using abundant brominated aromatic compounds, bis(pinacolate)diboron and potassium acetate by a ‘one-pot’ method. This process, which we believe proceeds via a Suzuki–Miyaura cross-coupling reaction mechanism, allows access to a variety of aromatic compounds under mild reaction conditions and has a good functional group tolerance with moderate to high yields.

Key words

self-coupling - Suzuki–Miyaura cross-coupling - palladium-carbon - catalysis - dimerization

• References and Notes

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• 22 General ProcedureTo a solution of brominated aromatic compounds (1 equiv), bis(pinacolate)diboron (1.5 equiv), and anhydrous ethanol (15 mL) was added palladium-carbon (0.01 equiv), followed by potassium acetate (3 equiv) under argon. The mixture was heated to 60 °C with stirring for the indicated time. The reactor was cooled to room temperature, and the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was extracted with dichloromethane (3 × 20 mL), and the organic layer was washed with water (2 × 20 mL) and once with brine (25 mL), dried over magnesium sulfate and concentrated in vacuo. The product was purified by flash column chromatography on silica gel using petroleum ether as eluent.Biphenyl (3a)Yield 0.97 g, 98.7%; pale solid; mp 69–71 °C (lit.^21a mp 69–71 ℃); R_f = 0.23 (PE). ¹H NMR (400 MHz, CDCl₃): δ = 7.60 (t, J = 1.24 Hz, 2 H), 7.44 (t, J = 7.20 Hz, 2 H), 7.34 (t, J = 7.36 Hz, 1 H). ¹³C NMR (150 MHz, CDCl₃): δ = 141.2, 128.7, 127.2, 127.1. GC–MS: m/z = 154.2.4,4′-Dimethyl-1,1′-biphenyl (3b)Yield 0.52 g, 98.1%; white solid; mp 125 ℃ (lit.^21b mp 125 ℃); R_f  = 0.50 (PE). ¹H NMR (600 MHz, CDCl₃): δ = 7.45 (d, J = 7.68 Hz, 2 H), 7.24 (d, J = 8.22 Hz, 2 H), 2.38 (s, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 138.3, 136.7, 129.4, 126.8, 21.1. GC–MS: m/z = 182.2.Benzerythrene (3c)Yield 0.20 g, 30.3%; white solid; mp > 300 ℃ (lit.^21c mp 315–318 °C); R_f = 0.57 (EtOAc/PE = 1:10). ¹H NMR (400 MHz, CDCl₃): δ = 7.77–7.37 (m, 18 H). ¹³C NMR (150 MHz, CDCl₃): δ = 140.7, 140.3, 139.6, 128.8, 127.6, 127.5, 127.1. GC–MS: m/z = 306.2.5,5,5′,5′,8,8,8′,8′-Octamethyl-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthalene (3d)Yield 0.35 g, 50.0%; colorless oily liquid; R_f = 0.41 (PE). ¹H NMR (400 MHz, CDCl₃): δ = 7.49 (s, 2 H), 7.48–7.32 (m, 4 H), 1.73 (s, 8 H), 1.35 (d, J = 5.08 Hz, 24 H). ¹³C NMR (150 MHz, CDCl₃): δ = 144.9, 143.5, 138.9, 126.7, 125.3, 124.5, 35.2, 35.1, 34.3, 34.1, 31.9, 31.8. GC–MS: m/z = 374.3.3,3′-Dimethoxy-1,1′-biphenyl (3e)Yield 0.38 g, 66.7%; colorless oily liquid (lit.^21d mp 36 ℃); R_f = 0.57 (EtOAc/PE = 1:5). ¹H NMR (600 MHz, CDCl₃): δ = 7.32 (t, J = 7.86 Hz, 2 H), 7.17–7.15 (m, 2 H), 7.11 (t, J = 2.22 Hz, 2 H), 6.88–6.86 (m, 2 H), 3.81 (s, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 159.9, 142.6, 129.7, 119.7, 112.9, 112.8, 55.2. GC–MS: m/z = 214.2.2,2′-Dimethoxy-1,1′-biphenyl (3f)Yield 0.50 g, 87.7%; white solid; mp 154–155 °C (lit.^21e mp154–155 ℃); R_f = 0.60 (EtOAc/PE = 1:3). ¹H NMR (400 MHz, CDCl₃): δ = 7.35–7.31 (m, 2 H), 7.26–7.02 (m, 2 H), 7.00 (q, J₁ = 7.44 Hz, J₂ = 6.60 Hz, 4 H), 3.77 (s, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 157.0, 131.4, 128.6, 127.8, 120.3, 111.1, 55.7. ESI-MS: m/z [M + H]⁺ = 215.1.2,2′-Biphenol (3g)Yield 0.41 g, 75.5%; colorless oily liquid (lit.^21f mp 50 °C); R_f = 0.35 (EtOAc/PE = 1:3). ¹H NMR (400 MHz, CDCl₃): δ = 7.38–7.33 (m, 2 H), 7.30 (d, J = 1.36 Hz, 1 H), 7.10–7.05 (q, J₁ = 1.00 Hz, J₂ = 8.64 Hz, 4 H), 5.40 (br, 2 H). ¹³C NMR (150 MHz, CDCl₃): δ = 152.0, 130.6, 129.2, 122.9, 120.9, 115.9. ESI-MS: m/z [M + H]⁺ = 184.9.4,4′-Biphenol (3h)Yield 0.86 g, 90.0%; white solid; mp 283 ℃ (lit.^21g mp 282–284 ℃); R_f = 0.50 (EtOAc/PE = 1:2). ¹H NMR (400 MHz, DMSO-d ₆): δ = 9.38 (s, 2 H), 7.37 (d, J = 8.52 Hz, 4 H), 6.79 (d, J = 8.52 Hz, 4 H). ¹³C NMR (150 MHz, DMSO-d ₆): δ = 155.7, 130.5, 126.3, 115.0. ESI-MS: m/z [M + H]⁺ = 184.9.4,4′-Bianiline (3i)Yield 0.50 g, 94.3%; brown solid; mp 117–119 °C (lit.^21h mp 80 ℃); R_f = 0.15 (EtOAc/PE = 1:3). ¹H NMR (400 MHz, CDCl₃): δ = 7.35 (d, J = 7.8 Hz, 4 H), 6.74 (d, J = 7.8 Hz, 4 H), 3.67 (s, 4 H). ¹³C NMR (150 MHz, DMSO-d ₆): δ = 146.2, 128.0, 125.4, 113.7. ESI-MS: m/z [M + H]⁺ = 185.1.3,3′-Diaminobiphenyl (3j)Yield (40 mg, 7.4%); brown solid; mp 89–90 °C (lit.²¹ⁱ mp 93 ℃); R_f = 0.26 (EtOAc/PE = 1:5). ¹H NMR (400 MHz, CDCl₃): δ = 7.22–7.16 (q, J₁ = 8.32 Hz, J₂ = 16.08 Hz, 2 H), 6.95 (d, J = 7.64 Hz, 2 H), 6.84 (s, 2 H), 6.64–6.62 (q, J ₁ = 1.44 Hz, J ₂ = 7.88 Hz, 2 H). ¹³C NMR (150 MHz, DMSO-d ₆): δ = 135.5, 133.7, 131.5, 115.4, 115.3, 112.7. ESI-MS: m/z [M+H]⁺ = 185.1.5,5′-Difluoro-2,2′-bipyridine (3k)Yield 0.54 g, 98.2%; off-white solid; mp 153–154 °C (lit.^21j mp 153–154 ℃); R_f = 0.87 (EtOAc/PE = 1:5). ¹H NMR (600 MHz, CDCl₃): δ = 8.50 (d, J = 2.34 Hz, 2 H), 8.39 (dd, J₁ = 4.38 Hz, J₂ = 8.76 Hz, 2 H), 7.54–7.51 (m, 2 H). ¹³C NMR (150 MHz, CDCl₃): δ = 160.7, 159.0, 151.4, 151.42, 137.3, 137.1, 123.9, 123.8, 122.3, 122.2. GC-MS: m/z = 192.2.2,2′-Bipyridine (3l)Yield 0.41 g, 41.8%; white solid; mp 72 °C (lit.^21k mp 71–72 ℃); R_f = 0.27 (EtOAc/PE = 1:5). ¹H NMR (600 MHz, CDCl₃): δ = 8.71 (d, J = 4.26 Hz, 2 H), 8.44 (d, J = 7.86 Hz, 2 H), 7.85 (t, J = 7.62 Hz, 2 H), 7.34 (t, J = 5.4 Hz, 2 H). ¹³C NMR (150 MHz, CDCl₃): δ = 156.0, 149.1, 137.1, 123.8, 121.2. ESI-MS: m/z [M + H]⁺ = 157.1.4,4′-Bis(methoxycarbonyl)biphenyl (3m)Yield 0.30 g, 48.4%); white solid; mp 224 °C (lit.^21l mp 224 ℃); R_f = 0.56 (EtOAc/PE = 1:5). ¹H NMR (400 MHz, CDCl₃): δ = 8.15 (d, J = 8.36 Hz, 4 H), 7.72 (q, J₁ = 8.40 Hz, J₂ = 1.60 Hz, 4 H), 3.97 (s, 6 H). ¹³C NMR (150 MHz, DMSO-d ₆): δ = 167.4, 143.7, 130.4, 129.1, 127.8, 52.7. GC–MS: m/z = 270.2.1,2-Diphenylethane (3n)Yield 0.83 g, 78.0%; white solid; mp 48–50 °C (lit.^21m mp 48–50 ℃); R_f = 0.37 (EtOAc/PE = 1:5). ¹H NMR (400 MHz, CDCl₃): δ = 7.28 (m, 5 H), 7.20 (m, 5 H), 2.92 (s, 4 H). ¹³C NMR (150 MHz, CDCl₃): δ = 141.8, 128.4, 128.3, 125.9, 37.9. GC–MS: m/z = 182.2.2-Naphthoic Acid (3o)Yield 0.68 g, 98.8%; white solid; mp 174–180 °C (lit.²¹ⁿ mp 180–183 ℃); R_f = 0.57 (EtOAc/PE/AcOH = 1:3:0.2). ¹H NMR (600 MHz, CDCl₃): δ = 8.74 (s, 1 H), 8.15 (d, J = 8.52 Hz, 1 H), 8.02 (d, J = 8.16 Hz, 1 H), 7.93 (t, J = 9.18 Hz, 2 H), 7.66–7.58 (m, 2 H). ¹³C NMR (150 MHz, CDCl₃): δ = 171.9, 136.0, 132.4, 132.2, 129.6, 128.7, 128.4, 127.8, 126.8, 126.4, 125.4. ESI-MS: m/z [M – H]^– = 170.9.Benzoic Acid (3p)Yield 0.47 g, 93.3%; white solid; mp 120–121 °C (lit.^21o mp 119–121 ℃); R_f = 0.60 (EtOAc/PE = 1:5). ¹H NMR (600 MHz, CDCl₃): δ = 8.13 (dd, J₁ = 1.02 Hz, J₂ = 8.10 Hz, 2 H), 7.63–7.61 (m, 1 H), 7.49 (t, J = 7.68 Hz, 2 H). ¹³C NMR (150 MHz, CDCl₃): δ = 172.4, 133.8, 130.2, 129.3, 128.5. ESI-MS: m/z [M – H]^– = 120.9.