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

• References and Notes

• 1a Davies J, Morcillo SP, Douglas JJ, Leonori D. Chem. Eur. J. 2018; 24: 12154
• 1b Rosa LD, Stasi RD, Longhitano L, D’Andrea LD. Bioorg. Chem. 2019; 91: 103160
• 1c Liu W.-X, Zhang C, Zhang H, Zhao N, Yu Z.-X, Xu J. J. Org. Chem. 2017; 139: 8678
• 2a Ren Z.-H, Zhang Z.-Y, Yang B.-Q, Wang Y.-Y, Guan Z.-H. Org. Lett. 2019; 13: 5394
• 2b Takai K, Katsura N, Kunisada Y. Chem. Commun. 2001; 1724
• 2c Corey EJ, Richman JE. J. Am. Chem. Soc. 1970; 92: 5276
• 3a Peng J, Zhi P, Yuan Z, Dan S, Hao Y, Xiao Q, Huang Y. Org. Lett. 2019; 21: 2658
• 3b Zard SZ. Chem. Soc. Rev. 2008; 37: 1603
• 4a Hirata Y, Nakamura S, Watanabe N, Kataoka O, Kurosaki T, Anada M, Hashimoto S. Chem. Eur. J. 2006; 12: 8898
• 4b Eckelbarger JD, Wilmot JT, Gin DY. J. Am. Chem. Soc. 2006; 128: 10370
• 4c Maggini M, Scorrano G, Prato M. J. Am. Chem. Soc. 1993; 115: 9798
• 5a Feng X.-H, Zhang G.-Z, Chen C.-Q, Yang M.-Y, Xu X.-Y, Huang G.-S. Synth. Commun. 2009; 39: 1768
• 5b Kumar SC. S, Kumar NV, Srinivas P, Bettadaiah BK. Synthesis 2014; 46: 1847
• 6a Chen X, Dam MA, Ono K, Mal A, Shen HS. R, Sheran NK, Wudl FA. Science 2002; 295: 1698
• 6b Obadia MM, Mudraboyina BP, Serghei A, Montarnal D, Drockenmuller E. J. Am. Chem. Soc. 2015; 137: 6078
• 6c Scott TF, Schneider AD, Cook WD, Bowman CN. Science 2005; 308: 1615
• 7 Ouattara M, Wein S, Calas M, Hoang YV, Vial H, Escale R. Med. Chem. Lett. 2007; 17: 593
• 8 El-Faham A, Khattab SN, Subirós-Funosas R, Albericio F. J. Pept. Sci. 2013; 20: 1
• 9 Gupta B, Sharma R, Singh N, Karpichev Y, Satnami ML, Ghosh KK. J. Phys. Org. Chem. 2013; 26: 632
• 10 Harger MJ. P. J. Chem. Soc., Perkin Trans. 1 1981; 3284
• 11 Sokolov VB, Ivanov AN, Epishina TA, Martynov IV. Bull. Acad. Sci. USSR Div. Chem. Sci. 1987; 36: 2401
• 12 Sokolov VB, Ivanov AN, Epishina TA, Goreva TV, Martynov IV. Bull. Acad. Sci. USSR Div. Chem. Sci. 1990; 39: 413
• 13 Wu SM, Zhang XH. J. Chem. Res. 2007; 3: 146
• 14 Hashemi SA, Khalili G. Monatsh. Chem. 2015; 146: 965
• 15 Zhu J.-L, Wu S.-T, Shie J.-Y. J. Org. Chem. 2014; 79: 3623
• 16 Russell GA, Ros F, Hershberger J, Tashtoush H. J. Org. Chem. 1982; 47: 1480
• 17a Jiang W, Huang Y, Zhou L, Zeng Q. Sci. China Chem. 2019; 62: 1213
• 17b Yang L, Feng J, Qiao M, Zeng Q. Org. Chem. Front. 2018; 5: 24
• 17c Zheng W, Tan M, Yang L, Zhou L, Zeng Q. Eur. J. Org. Chem. 2020; 1764
• 17d Tan M, Zheng W, Yang L, Zhou L, Zeng Q. Asian J. Org. Chem. 2019; 8: 2027
• 18a Kuchukulla RR, Li F, Zhou L, He Z, Zeng Q. Green Chem. 2019; 21: 5808
• 18b Jiang W, Li N, Zhou L, Zeng Q. ACS Catal. 2018; 8: 9899
• 18c Zhang L, Tan M, Zhou L, Zeng Q. Tetrahedron Lett. 2018; 59: 2778
• 19a Vessally E, Didehban K, Mohammadi R, Hosseinian A, Babazadeh M. J. Sulfur Chem. 2018; 39: 332
• 19b Detty MR, Zhou F, Friedman AE. J. Am. Chem. Soc. 1996; 118: 313
• 19c Huang H.-M, Li Y.-J, Ye Q, Yu W.-B, Han L, Jia J.-H, Gao J.-R. J. Org. Chem. 2014; 79: 1084
• 19d Pavlinac J, Zupan M, Stavber S. J. Org. Chem. 2006; 71: 1027
• 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.
• 24 Kawaguchi S.-i, Ogawa A. Org. Lett. 2010; 12: 1893
• 25 Hosseinian A, Farshbaf S, Fekri LZ, Nikpassand M, Vessally E. Curr. Top. Med. Chem. 2018; 376: 23