Catalytic Aerobic Photooxidation of Phosphines using Four-coordinated Organoboron Compounds as Photocatalysts

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.

Key words

photocatalysis - oxidation - phosphines - phosphine oxides - boron catalysis

Publication History

Received: 24 November 2023

Accepted after revision: 20 December 2023

Accepted Manuscript online:
20 December 2023

Article published online:
29 January 2024

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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): υ_max (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): υ_max (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): υ_max (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): υ_max (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.