Aerobic Photooxidative Synthesis of Phenols from Arylboronic Acids Using 2-Propanol as Solvent

Abstract

We report a useful method for the synthesis of phenols from arylboronic acids with hydrogen peroxide generated in situ by aerobic photooxidation. This reaction uses visible-light irradiation and easily handled 2-chloroanthraquinone as an organocatalyst under mild conditions, that is, an air atmosphere and ambient pressure and temperature. Because of this method’s metal- and base-free conditions, it represents an environmentally benign approach to the synthesis of phenols from arylboronic acids.

Key words

aerobic - boronic acid - phenol - photooxidation - visible light

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• 22 General Procedure A solution of arylboronic acid (0.3 mmol), 2-chloro-anthraquinone (0.05 equiv) in 2-PrOH (5 mL) in a Pyrex test tube in air atmosphere is stirred and irradiated externally with a 21 W fluorescent lamp for 20 h. The reaction mixture was concentrated in vacuo. Purification of the crude product by a silica gel column chromatography provided the product. 4-Chlorophenol (2a) Yield 31.7 mg, 82% (10 mmol scale: 1.17g, 91%); pale yellow solid. ¹H NMR (500 MHz, CDCl₃): δ = 7.19 (d, J = 8.9 Hz, 2 H), 6.77 (d, J = 8.9 Hz, 2 H), 4.94 (br s, 1 H); GC–MS (EI⁺): m/z = 128 [M]⁺, 100, 65. 4-Bromophenol (2b) Yield 39.7 mg, 76%; pale yellow oil. ¹H NMR (500 MHz, CDCl₃): δ = 7.33 (d, J = 8.9 Hz, 2 H), 6.72 (d, J = 8.9 Hz, 2 H), 5.31 (br s, 1 H). GC–MS (EI⁺): m/z = 174 [M]⁺, 172 [M]⁺, 93, 65. 4-Cyanophenol (2c) Yield 29.0 mg, 81%; colorless solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.56 (d, J = 8.7 Hz, 2 H), 6.94 (d, J = 8.7 Hz, 2 H), 6.73 (br s, 1 H). DART-MS: m/z = 120.04 [M + H]⁺. 4-(Trifluoromethyl)phenol (2d) Yield 30.4 mg, 63%; colorless oil. ¹H NMR (500 MHz, CDCl₃): δ = 7.52 (d, J = 8.4 Hz, 2 H), 6.90 (d, J = 8.4 Hz, 2 H), 5.63 (br s, 1 H). GC–MS (EI⁺): m/z = 162 [M]⁺, 143, 112. 4-Nitrophenol (2e) Yield 40.9 mg, 98%; pale yellow solid. ¹H NMR (400 MHz, DMSO-d ₆): δ = 11.09 (br s, 1 H), 8.14 (d, J = 8.9 Hz, 2 H), 6.95 (d, J = 8.9 Hz, 2 H). GC–MS (EI⁺): m/z = 139 [M]⁺, 109, 65. 3-Nitrophenol (2f) Yield 40.3 mg, 97%; pale yellow solid. ¹H NMR (500 MHz, DMSO-d ₆): δ = 10.46 (s, 1 H), 7.67 (dd, J = 7.8, 2.3 Hz, 1 H), 7.56 (t, J = 2.3 Hz, 1 H), 7.47 (t, J = 7.8 Hz, 1 H), 7.22 (dd, J = 7.8, 2.3 Hz, 1 H). GC–MS (EI⁺): m/z = 139 [M]⁺, 93, 65. 4-Hydroxybenzoic Acid (2g) Yield 32.9 mg, 79%; colorless solid. ¹H NMR (500 MHz, DMSO-d ₆): δ = 7.80 (d, J = 8.6 Hz, 2 H), 6.84 (d, J = 8.6 Hz, 2 H). GC–MS (EI⁺): m/z = 138 [M]⁺, 121, 93. 4-Hydroxymethyl Benzoate (2h) Yield 37.7 mg, 83%; colorless solid. ¹H NMR (500 MHz, CDCl₃): δ = 7.95 (d, J = 8.9 Hz, 2 H), 6.89 (d, J = 8.9 Hz, 2 H), 6.42 (br s, 1 H), 3.90 (s, 3 H). DART-MS: m/z = 153.06 [M + H]⁺. 4-Hydroxybenzaldehyde (2i) Yield 26.9 mg, 73%; colorless solid. ¹H NMR (500 MHz, CDCl₃): δ = 9.86 (s, 1 H), 7.83 (d, J = 8.6 Hz, 2 H), 6.99 (d, J = 8.6 Hz, 2 H), 6.49 (br s, 1 H). DART-MS: m/z = 123.04 [M + H]⁺. 4-tert-Butylphenol (2j) Yield 41.9 mg, 93%; colorless solid. ¹H NMR (500 MHz, CDCl₃): δ = 7.25 (d, J = 8.5 Hz, 2 H), 6.77 (d, J = 8.5 Hz, 2 H), 5.11 (br s, 1 H), 1.29 (s, 9 H). GC–MS (EI⁺): m/z = 150 [M]⁺, 135, 107. 4-Methoxyphenol (2k) Yield 31.2 mg, 83%; colorless solid. ¹H NMR (500 MHz, CDCl₃): δ = 6.77 (m, 4 H), 5.48 (br s, 1 H), 3.76 (s, 3 H). DART-MS: m/z = 125.06 [M + H]⁺. 2,6-Dimethylphenol (2l) Yield 19.2 mg, 52%; colorless solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.19 (d, J = 8.9 Hz, 2 H), 6.77 (d, J = 8.9 Hz, 1 H), 4.63 (s, 1 H), 2.25 (s, 6 H). GC–MS (EI⁺): m/z = 122 [M]⁺, 107, 91. 2-Naphthol (2m) Yield 31.1 mg, 72%; pale yellow solid. ¹H NMR (500 MHz, CDCl₃): δ = 7.75 (t, J = 9.2 Hz, 2 H), 7.67 (d, J = 8.6 Hz, 1 H), 7.42 (t, J = 7.7 Hz, 1 H), 7.32 (t, J = 7.2 Hz, 2 H), 7.13 (d, J = 2.9 Hz, 1 H), 7.09 (dd, J = 8.6, 2.3 Hz, 1 H), 5.13 (s, 1 H). DART-MS: m/z = 145.07 [M + H]⁺. 3-Hydroxypyridine (2n) Yield 15.2 mg, 53%; colorless solid. ¹H NMR (500 MHz, CDCl₃): δ = 8.29 (d, J = 3.0 Hz, 1 H), 8.09 (dd, J = 5.0, 1.5 Hz, 1 H), 7.33 (m, 1 H), 7.29 (dd, J = 8.0, 5.0 Hz, 1 H). GC–MS (EI⁺): m/z = 95 [M]⁺, 67, 39.