Aerobic Photooxidative Cleavage of Vicinal Diols to Carboxylic Acids Using 2-Chloroanthraquinone

Abstract

We developed the aerobic photooxidative cleavage of vicinal diols to carboxylic acids using 2-chloroanthraquinone in the presence of photoirradiation with a high-pressure mercury lamp. This is the first metal-free reaction using molecular oxygen as the terminal oxidant.

Key words

photooxidation - aerobic - anthraquinone - vicinal diol - carboxylic acid

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• 9 General Procedure A solution of 1-phenyl-1,2-ethanediol (1a, 0.3 mmol) and 2-chloroanthraquinone (0.03 mmol) in dry EtOAc (3 mL) in a Pyrex test tube, purged with an O₂ balloon, was stirred and irradiated externally with a 400 W high-pressure mercury lamp for 20 h. The reaction mixture was concentrated in vacuo, and 1% aq NaOH was added. The aqueous solution was washed with Et₂O, and then acidified with 2 M aq HCl solution, which was extracted with Et₂O. The organic layer was washed with brine and dried over MgSO₄, and concen-trated in vacuo. Purification of the crude product by PTLC (CHCl₃–MeOH = 9:1) provided benzoic acid (R_f = 0.6, 31.4 mg, 86%). Benzoic Acid (2a) ¹H NMR (400 MHz, CDCl₃): δ = 8.13 (d, J = 7.4 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H), 7.48 (t, J = 7.4 Hz, 2 H). ¹³C NMR (100 MHz, acetone-d ₆): δ = 172.6, 133.9, 130.3, 129.4, 128.6. 4-Chlorobenzoic Acid (2b) ¹H NMR (500 MHz, acetone-d ₆): δ = 8.01 (d, J = 8.6 Hz, 2 H), 7.53 (d, J = 8.6 Hz, 2 H). ¹³C NMR (100 MHz, acetone-d ₆): δ = 166.7, 139.5, 132.1, 130.3, 129.5. 4-tert-Butylbenzoic Acid (2c) ¹H NMR (500 MHz, CDCl₃): δ = 8.06 (d, J = 8.7 Hz, 2 H), 7.49 (d, J = 8.7 Hz, 2 H), 1.35 (s, 9 H). ¹³C NMR (125 MHz, CDCl₃): δ = 172.6, 157.7, 130.2, 126.7, 125.6, 35.3, 31.2. 4-Methoxybenzoic Acid (2d) ¹H NMR (500 MHz, acetone-d ₆): δ = 7.96 (d, J = 9.2 Hz, 2 H), 7.00 (d, J = 9.2 Hz, 2 H), 3.85 (s, 3 H). ¹³C NMR (100 MHz, acetone-d ₆): δ = 167.5, 164.4, 132.5, 123.7, 114.5, 55.8. 2-Naphthoic Acid (2g) ¹H NMR (400 MHz, acetone-d ₆): δ = 8.66 (s, 1 H), 8.07 (dd, J = 8.5, 1.7 Hz, 2 H), 7.99 (dd, J = 8.5, 5.6 Hz, 2 H), 7.66–7.57 (m, 2 H). ¹³C NMR (100 MHz, acetone-d ₆): δ = 168.9, 134.9, 134.2, 132.3, 131.3, 129.4, 128.4, 127.9, 127.0, 126.7, 125.5. Benzophenone (2h) ¹H NMR (500 MHz,CDCl₃): δ = 7.80 (d, J = 8.0 Hz, 4 H), 7.58 (t, J = 8.0 Hz, 2 H), 7.48 (t, J = 8.0 Hz, 4 H). ¹³C NMR (125 MHz, CDCl₃): δ = 196.8, 137.8, 132.5, 130.2, 128.4. Nonanoic Acid (2i) ¹H NMR (500 MHz,CDCl₃): δ = 2.35 (t, J = 7.6 Hz, 2 H), 1.70–1.60 (m, 2 H), 1.39–1.22 (m, 10 H), 0.89 (t, J = 6.9 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 181.0, 34.5, 32.2, 29.6, 29.5, 29.5, 25.1, 23.1, 14.5. Undecanoic Acid (2j) ¹H NMR (500 MHz,CDCl₃): δ = 2.35 (t, J = 7.5 Hz, 2 H), 1.66–1.59 (m, 2 H), 1.35–1.21 (m, 14 H), 0.88 (t, J = 6.6 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 179.8, 32.0, 29.6, 29.5, 29.4, 29.3, 29.2, 29.1, 24.7, 22.7, 14.2. Tridecanoic Acid (2k) ¹H NMR (500 MHz,CDCl₃): δ = 2.35 (t, J = 7.5 Hz, 2 H), 1.65–1.55 (m, 2 H), 1.34–1.20 (m, 18 H), 0.88 (t, J = 6.9 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 179.8, 33.8, 31.6, 29.4, 29.3, 29.2, 29.1, 29.0, 28.8, 24.4, 22.4, 13.8. Adipic Acid (2l) ¹H NMR (500 MHz, DMSO-d ₆): δ = 2.22–2.18 (m, 4 H), 1.52–1.47 (m, 4 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 174.5, 33.5, 24.2.