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Synlett 2024; 35(14): 1698-1702
DOI: 10.1055/a-2233-9431
DOI: 10.1055/a-2233-9431
letter
Catalytic Aerobic Photooxidation of Phosphines using Four-coordinated Organoboron Compounds as Photocatalysts
We are grateful for financial support from the National Natural Science Foundation of China (Nos. 22061036 and 21963010). The authors also thank the Program for Youth Science and Technology Innovation Leaders of Xinjiang Bingtuan (2019CB026), the Program for Changjiang Scholars and Innovative Research Team in University (IRT_15R46), and the Yangtze River Scholar Research Project of Shihezi University (CJXZ201601).
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Abstract
A photooxidation approach to the conversion of phosphines into the corresponding phosphine oxides is reported. By taking advantage of O2 in the air as an oxidant and oxygen source, phosphine oxides were obtained efficiently in moderate to excellent yields. A four-coordinated organoboron compound was used as the photocatalyst to activate O2 to its singlet state. This photooxidation method features mild reaction conditions, broad functional-group tolerance, and a wide substrate scope.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2233-9431.
- Supporting Information
Publication History
Received: 24 November 2023
Accepted after revision: 20 December 2023
Accepted Manuscript online:
20 December 2023
Article published online:
29 January 2024
© 2024. Thieme. All rights reserved
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- 20 Phosphine Oxides 2a–af; General Procedure A flame-dried 25 mL quartz-column reaction tube equipped with a magnetic stirrer bar was charged with the appropriate phosphine 1 (0.2 mmol, 1.0 equiv), AQDAB (0.002 mmol, 1 mol%), and CH3CN (2.0 mL). The tube was placed in a photocatalytic parallel reactor equipped with a white LEDs light source (5 W) at the bottom. The mixture was then irradiated at a distance of ~0.3 cm from the light source with stirring for 3 h at 25 °C. The resulting mixture was concentrated under a vacuum to afford a crude product, which was purified by column chromatography (silica gel, PE–EtOAc). Tris(3-chlorophenyl)phosphine Oxide (2h) Prepared by following the general procedure from tris(3-chlorophenyl) phosphine (1h; 73 mg, 0.20 mmol) as a solid; yield: 95%; mp 135.3–136.6 °C. IR ((KBr): υmax (cm-1)): 3066, 1562, 1463, 1402, 1193, 1136, 1076, 788, 688, 665, 568 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 12.4 Hz, 3 H), 7.53–7.51 (m, 3 H), 7.49–7.46 (m, 3 H), 7.43–7.39 (m, 3 H). 13C NMR (101 MHz, CDCl3): δ = 135.4 (d, J = 16.0 Hz), 134.1, 133.1, 132.7 (d, J = 2.6 Hz), 131.8 (d, J = 10.9 Hz), 130.3 (d, J = 13.3 Hz), 130.0 (d, J = 9.6 Hz). 31P NMR (162 MHz, CDCl3): δ = 25.84. HRMS (APCI): m/z [M + H]+ calcd for C18H13Cl3OP: 380.9764; found: 380.9760. Tris(3-fluorophenyl)phosphine Oxide (2i) Prepared by following the general procedure from tris(3-fluorophenyl)phosphine (1i; 163 mg, 0.20 mmol) as a solid; yield: 99%; mp 94.7–102.5 °C. IR ((KBr): υmax (cm-1)): 1579, 1475, 1421, 1269, 1228, 1186, 1099, 894, 792, 696, 586, 501 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.37 (t, J = 10.0 Hz, 6 H), 7.29 (d, J = 7.6 Hz, 6 H). 13C NMR (101 MHz, CDCl3): δ = 162.5 (dd, J = 252.1, 17.0 Hz), 130.8 (dd, J = 14.2, 7.4 Hz), 127.7 (dd, J = 9.0, 3.0 Hz), 119.7 (d, J = 21.2 Hz), 118.9 (dd, J = 22.6, 10.6 Hz). 19F NMR (376 MHz, CDCl3): δ = –110.25. 31P NMR (162 MHz, CDCl3): δ = 25.94. HRMS (APCI): m/z [M + H]+ calcd for C18H13F3OP: 333.0650; found: 333.0647. Tris(3,5-dimethylphenyl)phosphine Oxide (2p) Prepared by following the general procedure from tris(3,5-dimethylphenyl)phosphine (1p; 72 mg, 0.20 mmol) as a solid; yield: 92%; mp 205.0–205.8 °C. IR ((KBr): υmax (cm-1)): 2916, 2854, 1598, 1456, 1274, 1193, 1124, 871, 852, 694, 584 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.30 (d, J = 12.0 Hz, 6 H), 7.13 (s, 3 H), 2.31 (s, 18 H). 13C NMR (101 MHz, CDCl3): δ = 138.0 (d, J = 12.7 Hz), 133.5 (d, J = 2.8 Hz), 132.6 (d, J = 103.1 Hz), 129.0 (d, J = 9.8 Hz), 21.3. 31P NMR (162 MHz, CDCl3): δ = 29.68. HRMS (APCI): m/z [M + H]+ calcd for C24H28OP: 363.1872; found: 363.1868. Triethyl Phosphate (2ac) Prepared by following the general procedure from triethyl phosphite (1ac; 36 mg, 0.20 mmol) as a colorless oil; yield: 73%. IR ((neat): υmax (cm-1)): 2929, 2852, 1446, 1274, 1157, 1041, 972, 800, 545 cm–1. 1H NMR (400 MHz, CDCl3): δ = 4.03–3.99 (m, 6 H), 1.24 (t, J = 7.2 Hz, 9 H). 13C NMR (101 MHz, CDCl3): δ = 63.5 (d, J = 5.9 Hz), 16.0 (d, J = 6.7 Hz). 31P NMR (162 MHz, CDCl3): δ = 1.02. HRMS (APCI): m/z [M + H]+ calcd for C6H16O4P: 183.0780; found: 183.0778.