Visible-Light-Mediated Facile Reductive Aromatization of Quinols

Abstract

A range of phenols bearing multiple useful functionalities at their meta positions were prepared from the corresponding quinols under the cooperative effects of visible light irradiation, Ru(bpy)₃Cl₂ photosensitizer, Hünig’s base, LiBF₄, and MeCN solvent. The process involves visible-light-enabled photocatalytic cleavage of C–O bond as the strategic event.

Key words

visible light - photocatalysis - amine - C–O bond cleavage - aromatization

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• 9 General Procedure for Visible-Light-Mediated Facile Reductive Aromatization of Quinols: A flame-dried round-bottom flask (10 mL) was equipped with magnetic stirring bar and charged with quinol compound (0.1 mmol, 1.0 equiv), tris(2,2′-bipyridyl)ruthenium(II) chloride hexahydrate (0.005 mmol, 0.05 equiv), LiBF₄ (0.2 mmol, 2.0 equiv) and MeCN (2.0 mL). To the mixture was then added amine (0.5 mmol, 5.0 equiv), and it was irradiated by a household bulb (45 W) under a balloon argon atmosphere at r.t. until the starting material disappeared from the TLC. The reaction mixture was filtrated through celite and washed with Et₂O. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to afford the pure product. (Z)-3-(3-Hydroxy-1-phenylprop-1-en-1-yl)-4-methylphenol (4a): colorless liquid; yield: 23.3 mg (97%). ¹H NMR (500 MHz, CDCl₃): δ = 7.13–7.30 (m, 5 H), 7.02 (d, J = 8.2 Hz, 1 H), 6.75 (dd, J = 8.2, 2.7 Hz, 1 H), 6.62 (d, J = 2.7 Hz, 1 H), 6.29 (t, J = 6.9 Hz, 1 H), 4.27 (s, 2 H), 4.02 (d, J = 5.9 Hz, 2 H), 1.89 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 153.76 (s), 143.13 (s), 139.95 (s), 139.30 (s), 131.35 (s), 128.35 (s), 128.18 (s), 127.59 (s), 126.70 (s), 126.46 (s), 116.64 (s), 114.83 (s), 60.84 (s), 18.59 (s). HRMS: m/z [M + Na⁺] calcd for C₁₆H₁₆NaO₂: 263.1048; found: 263.1041. (Z)-2-(3-Hydroxy-1-phenylprop-1-en-1-yl)-[1,1′-biphenyl]-4-ol (4d): white solid; yield: 27.2 mg (90%). ¹H NMR (500 MHz, MeOD): δ = 7.21 (d, J = 8.4 Hz, 1 H), 7.06–7.17 (m, 10 H), 6.89 (dd, J = 8.4, 2.6 Hz, 1 H), 6.69 (d, J = 2.6 Hz, 1 H), 6.06 (t, J = 6.4 Hz, 1 H), 4.00–4.14 (m, 1 H), 3.80 (dd, J = 13.2, 5.3 Hz, 1 H). ¹³C NMR (126 MHz, acetone): δ = 156.51 (s), 141.53 (s), 141.29 (s), 140.95 (s), 138.76 (s), 133.35 (s), 131.26 (s), 129.30 (s), 128.78 (s), 127.92 (s), 127.56 (s), 126.89 (s), 126.66 (s), 126.12 (s), 117.41 (s), 115.05 (s), 60.17 (s). HRMS: m/z [M + Na⁺] calcd for C₂₁H₁₈NaO₂: 325.1204; found: 325.1200. (Z)-3-{1-([1,1′-Biphenyl]-4-yl)-3-hydroxyprop-1-en-1-yl}-4-methylphenol (4l): white solid; yield: 25.6 mg (81%). ¹H NMR (500 MHz, CDCl₃): δ = 7.53 (d, J = 7.4 Hz, 2 H), 7.44 (d, J = 8.3 Hz, 2 H), 7.39 (t, J = 7.6 Hz, 2 H), 7.32 (t, J = 7.3 Hz, 1 H), 7.25 (d, J = 8.3 Hz, 2 H), 7.05 (d, J = 8.3 Hz, 1 H), 6.78 (dd, J = 8.2, 2.6 Hz, 1 H), 6.67 (d, J = 2.6 Hz, 1 H), 6.36 (t, J = 6.9 Hz, 1 H), 3.98–4.10 (m, 2 H), 1.92 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 153.85 (s), 143.02 (s), 140.50 (s), 140.33 (s), 139.09 (s), 138.79 (s), 131.44 (s), 128.79 (s), 128.14 (s), 127.35 (s), 127.03 (s), 126.92 (s), 126.87 (s), 126.27 (s), 116.58 (s), 114.98 (s), 60.78 (s), 18.68 (s). HRMS: m/z [M + Na⁺] calcd for C₂₂H₂₀NaO₂: 339.1361; found: 339.1357. (Z)-3-[1-(3,4-Dimethylphenyl)-3-hydroxyprop-1-en-1-yl]-4-methylphenol (4o): colorless liquid; yield: 23.0 mg (86%). ¹H NMR (400 MHz, CDCl₃): δ = 6.99–7.13 (m, 3 H), 6.94 (d, J = 7.9 Hz, 1 H), 6.75 (dd, J = 8.2, 2.7 Hz, 1 H), 6.59 (d, J = 2.6 Hz, 1 H), 6.31 (t, J = 6.8 Hz, 1 H), 4.04 (d, J = 6.8 Hz, 2 H), 2.23 (s, 3 H), 2.21 (s, 3 H), 1.97 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 153.5 (s), 142.9 (s), 138.9–139.5 (m), 137.5 (s), 136.4 (s), 136.2 (s), 131.2 (s), 129.6 (s), 128.2 (s), 127.5 (s), 125.7 (s), 124.0 (s), 116.5 (s), 114.5 (s), 60.9 (s), 19.8 (s), 19.4 (s), 18.6 (s). HRMS: m/z [M + Na⁺] calcd for C₁₈H₂₀NaO₂: 291.1361; found: 291.1354.