I₂-Catalyzed Oxidative Coupling of Ketone Oximes and Dialkyl/Diarylphosphine Oxides

Abstract

A new protocol for the oxidative coupling of ketone oximes with dialkyl/diarylphosphine oxides to synthesize O-(dialkylphosphinyl)ketone oximes has been developed. Hydrogen peroxide is used as a green oxidizing agent, and molecular iodine is used as a nonmetal catalyst. The reaction has a high atom economy, with water as the only byproduct. O-(Dialkylphosphinyl)ketone oximes with 26 examples have been obtained with high yields. Furthermore, the product may be transformed into other molecules, i.e., by reduction.

Key words

ketone oximes - di[alkyl/(hetero)aryl]phosphine oxides - O-(dialkylphosphinyl)ketone oximes - oxidative coupling - molecular iodine - synthetic method

Publication History

Received: 08 August 2020

Accepted after revision: 31 August 2020

Article published online:
08 October 2020

• References and Notes

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• 20 General Procedure for I₂-Catalyzed Oxidative Coupling of Ketone Oximes and Dialkyl/Diarylphosphine Oxides A 25 mL test tube equipped with a magnetic stirrer was charged with ketone oxime (0.5 mmol), dialkyl/diarylphosphine oxide (0.6 mmol), H₂O₂ (0.6 mmol), I₂ (5 mol%) and acetonitrile (2 mL). After the test tube was directly sealed in air with a sleeve stopper septum, the reaction mixture was stirred at 40 °C for 4 h in air. After cooled to room temperature, the reaction mixture was quenched by the addition of saturated Na₂S₂O₃ solution (10 mL). The reaction mixture was extracted with ethyl acetate (3 × 15 mL). The combined organic phase was dried over MgSO₄, filtered, and concentrated in vacuum on a rotary evaporator. The resulting residue was purified by silica gel flash chromatography, eluting with EtOAc/petroleum ether (3:7 to 5:5), to afford the desired products 3.
• 21 Analytical Data for O-(diphenylphosphinoyl)-5-fluoro-1-indanone oxime (3b) White solid (164 mg, 90%); mp 171–174 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.89 (ddd, J = 12.3, 8.3, 1.4 Hz, 4 H), 7.63 (dd, J = 8.6, 5.3 Hz, 1 H), 7.58–7.52 (m, 2 H), 7.51–7.40 (m, 4 H), 6.99 (dd, J = 8.7, 2.2 Hz, 1 H), 6.92 (td, J = 8.8, 2.4 Hz, 1 H), 3.21–3.13 (m, 2 H), 3.11–2.98 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 170.54, 170.42, 166.57, 164.06, 152.06, 151.97, 132.31, 132.28, 132.14, 132.04, 131.40, 130.50, 130.04, 128.55, 128.41, 124.93, 124.83, 115.27, 115.04, 112.45, 112.23, 28.42, 28.40, 28.17. ³¹P NMR (162 MHz, CDCl₃): δ = 34.93. HRMS (ESI-TOF): m/z [M + H]⁺ calcd for C₂₁H₁₈FNO₂P: 366.1059; found: 366.1066. HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₂₁H₁₇FNO₂NaP: 388.0878; found: 388.0851.
• 22 Procedure for the Reduction of O-(Diphenylphosphino)indanone Oxime (3a) A 25 mL test tube equipped with a magnetic stirrer was charged with O-(diphenylphosphinyl)indanone oxime (3a, 1 mmol) and sodium borohydride (3 mmol), acetonitrile (2 mL). After the test tube was directly sealed in air with a sleeve stopper septum, the reaction mixture was stirred at 60 °C for 6 h in air. After cooled to room temperature, the reaction mixture was quenched by the addition of saturated NaCl solution (10 mL). The reaction mixture was extracted with ethyl acetate (3 × 15 mL). The combined organic phase was dried over MgSO₄, filtered, and concentrated in vacuum on a rotary evaporator. The resulting residue was purified by silica gel flash chromatography, eluting with EtOAc/petroleum ether (3:7), to afford the desired product 4.
• 23 Analytical Data for {[(2,3-Dihydro-1H-inden-1-yl)amino[oxy}diphenylphosphine Oxide (4) White solid (151 mg, 87%); mp 141–144 °C. ¹H NMR (400 MHz, CDCl₃) δ = 7.95–7.83 (m, 4 H), 7.66 (d, J = 7.8 Hz, 1 H), 7.54 (td, J = 7.5, 1.2 Hz, 2 H), 7.47 (td, J = 7.4, 3.6 Hz, 4 H), 7.38 (t, J = 7.2 Hz, 1 H), 7.32 (d, J = 7.6 Hz, 1 H), 7.21 (t, J = 7.4 Hz, 1 H), 3.15 (dd, J = 7.8, 4.0 Hz, 2 H), 3.12–3.04 (m, 2 H). 13C NMR (101 MHz, CDCl₃) δ = 171.81, 171.69, 149.52, 134.43, 132.25, 132.23, 132.16, 132.06, 131.79, 131.51, 130.16, 128.52, 128.39, 127.08, 125.57, 123.20, 30.20, 29.71, 28.40, 27.77. ³¹P NMR (162 MHz, CDCl₃) δ = 29.54. HRMS (ESI-TOF) m/z: [M+H]⁺ calcd for C₂₁H21NO2P [M+H]⁺ 350.1309; found: 350.1895.
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