Catalyst-Free Oxidation of Sulfides to Sulfoxides by gem-Dihydroperoxide under Mild Conditions

Abstract

A facile and efficient method for the oxidation of sulfides (dialkyl, phenylalkyl, benzylalkyl) to sulfoxides under mild conditions without using any catalysts is reported. This method afforded a series of sulfoxides with good yields (>95%). The ready accessibility and low cost of the gem-dihydroperoxides will endow it with attractive applications in chemical synthesis as oxidants.

Key words

sulfides - sulfoxides - gem-dihydroperoxides - oxidation - catalyst-free

• References and Notes

• 1a Terent’ev AO, Platonov MM, Kutkin AV. Cent. Eur. J. Chem. 2006; 4: 207
• 1b Peroxide Chemistry: Mechanistic and Preparative Aspects of Oxygen Transfer. Adam W. Wiley-VCH; Weinheim: 2000
• 1c Cosijn AH. M, Ossewold MG. J. Recl. Trav. Chim. Pays-Bas 1968; 87: 1264
• 1d Terent’ev AO, Platonov MM, Ogibin YN, Nikishin GI. Synth. Commun. 2007; 37: 1281
• 2a Handbook of Vinyl Polymers: Radical Polymerization, Process, and Technology, 2nd ed. Mishra M, Yagci Y. CRC Press; Boca Raton: 2008
• 2b Sheppard CS, Kamath VR. Polym. Eng. Sci. 1979; 19: 597
• 3a Todorović NM, Stefanović M, Tinant B, Declercq J.-P, Makler MT, Šolaja BA. Steroids 1996; 61: 688
• 3b Žmitek K, Zupan M, Iskra J. Org. Biomol. Chem. 2007; 5: 3895
• 3c Tropina VI, Krivykh OV, Sadchikova NP, Terent’ev AO, Krylov IB. Pharm. Chem. J. 2010; 44: 248
• 4 Selvam JJ. P, Suresh V, Rajesh K, Babu C, Suryakiran N, Venkateswarlu Y. Tetrahedron Lett. 2008; 49: 3463
• 5a Hogan P, Hopes P, Moss W, Robinson G, Patel I. Org. Process Res. Dev. 2002; 6: 225
• 5b Siegert M, Knittel C, Süssmuth R. Angew. Chem. Int. Ed. 2020; 59: 5500
• 5c Xie D, Wang Y, Zhang X, Fu Z, Niu D. Angew. Chem. Int. Ed. 2022; 61: e202204922
• 5d Richter J, Kahrilas P, Johanson J, Maton P, Breiter J, Wang C, Marino V, Hamelin B, Levine J, Investigators E. Am. J. Gastroenterol. 2001; 96: 656
• 5e Zhang J, Wei C, Li S, Hu D, Song B. Pestic. Biochem. Physiol. 2020; 167: 104605
• 6a Murray RW, Jeyaraman R, Pillay MK. J. Org. Chem. 1987; 52: 746
• 6b Adam W, Golsch D. Chem. Ber. 1994; 127: 1111
• 6c Adam W, Golsch D, Hadjiarrpoglou L, Lévai A, Nemes C, Patonay T. Tetrahedron 1994; 50: 13113
• 7a Patek M, Drake B, Lebel M. Tetrahedron Lett. 1995; 36: 2227
• 7b Oae S, Takata T, Kim YH. Bull. Chem. Soc. Jpn. 1982; 55: 2484
• 7c Ali MH, Stevens WC. Synthesis 1997; 764
• 7d Vostrikov NS, Spirikhin LV, Lobov AN, Gimazetdinov AM, Zileeva ZR, Vakhitova YV. Mendeleev Commun. 2019; 29: 372
• 8 Kluge R, Schulz M, Liebsch S. Tetrahedron 1996; 52: 5773
• 9 Sylvian S, Wanger A, Mioskowosky C. Tetrahedron Lett. 1997; 38: 1043
• 10 Kowalski P, Mitka K, Ossowska K, Kolarska Z. Tetrahedron 2005; 61: 1933
• 11a Kaczorowska K, Kolarska Z, Mitka K, Kowalski P. Tetrahedron 2005; 61: 8315
• 11b Li X, Wang Y, Yang L, Zhang Z, Xie X. Tetrahedron 2022; 110: 132708
• 11c Skolia E, Gkizis PL, Kokotos CG. ChemPlusChem 2022; 87: e202200008
• 12a Bagherzadeh M, Tahsini L, Latifi R. Catal. Commun. 2008; 9: 1600
• 12b Bagherzadeh M, Zare M. J. Sulfur Chem. 2011; 32: 335
• 12c Zakavi S, Abasi A, Pourali AR, Talebzadeh S. Bull. Korean Chem. Soc. 2012; 3: 35
• 12d Rayati S, Nejabat F, Zakavi S. Inorg. Chem. Commun. 2014; 40: 82
• 13 Andriyashina NM, Grabovskii SA, Safiullin RL. Lett. Org. Chem. 2023; in press
• 14a Bunge A, Hamann H.-J, Dietz D, Liebscher J. Tetrahedron 2013; 69: 2446
• 14b Bunge A, Hamann H.-J, McCalmont E, Liebscher J. Tetrahedron Lett. 2009; 50: 4629
• 15a Hauser SA, Cokoja M, Kühn FE. Catal. Sci. Technol. 2013; 3: 552
• 15b Xia Q.-H, Ge H.-Q, Ye C.-P, Liu Z.-M, Su K.-X. Chem. Rev. 2005; 105: 1603
• 16 Jiang X, Yao C, Tong C, Bai R, Zhou T, Xie Y. Chin. J. Org. Chem. 2020; 40: 1752
• 17 General Method for the Preparation of Sulfoxides Sulfide 2–12 (1 mmol) was dissolved in an appropriate solvent, and a gem-dihydroperoxide 1a ^1d (0.6 mmol) solution in the same solvent was added. The reaction mass was left protected from light. The reaction progress was monitored by TLС or HPLC. At the end of the reaction, the solvent was evaporated and purification by flash chromatography on silica gel was performed. Methyl Pentyl Sulfoxide (2a) Colorless oil. IR: ν_max = 2957, 2930, 2860, 1466, 1423, 1379, 1303, 1022, 962, 941, 729, 694 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.87–2.72 (m, 2 H, SCH₂), 2.621 (s, 3 H, SCH₃), 1.82–1.68 (m, 2 H, C²H₂), 1.54–1.34 (m, 4 H, C³,⁴H₂), 0.944 (t, J  = 7.15  Hz, 3 H, CH₂CH ₃). ¹³C NMR (125 MHz, СD₃OD): δ = 54.86 (SCH₂), 38.10 (SCH₃), 31.90 (C³H₂), 23.34 (C²,⁴H₂), 14.17 (CH₂ CH₃). HRMS: m/z calcd for C₆H₁₅OS [M + H]: 135.0844; found: 135.0841. Anal. Calcd (%): C, 53.68; H, 10.51, S, 23.89%. Found: C, 53.73; H, 10.32; S, 24.0. Methyl Heptyl Sulfoxide (3a) Colorless oil. IR: ν_max = 2954, 2927, 2856, 1466, 1417, 1379, 1304, 1034, 943, 723, 692 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 2.76–2.68 (m, 1 H, SCH₂), 2.67–2.58 (m, 1 H, SCH₂), 2.538 (s, 3 H, SCH₃), 1.73–1.65 (m, 2 H, C²H₂), 1.48–1.34 (m, 2 H, C⁶H₂), 1.34–1.19 (m, 6 H, C^3–5H₂), 0.838 (t, J  = 6.75  Hz, 3 H, CH₂CH ₃). ¹³C NMR (125 MHz, CDCl₃): δ = 54.56 (SCH₂), 38.33 (SCH₃), 31.45 (CH₂), 28.77 (CH₂), 28.66 (CH₂), 22.50 (C²H₂), 22.45 (C⁶H₂), 13.94 (CH₂ CH₃). HRMS: m/z calcd for C₈H₁₉OS [M + H]: 163.1157; found: 163.1166. Anal. Calcd (%): C, 59.21; H, 11.18; S, 19.76. Found: C, 59.09; H, 11.13; S, 19.79. Diheptyl Sulfoxide (4a) White crystals, mp 66 °C. IR: ν_max = 2953, 2912, 2852, 1463, 1377, 1010, 989 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.84–2.70, (m, 4 H, C¹H₂), 1.81–1.69 (m, 4 H, C²H₂), 1.54–1.41 (m, 4 H, C³H₂), 1.41–1.27 (m, 12 H, C^4–6H₂), 0.910 (t, J  = 6.8 Hz, 6 H, CH₃). ¹³C NMR (125 MHz, СD₃OD): δ = 52.82 (C¹H₂), 32.76 (C⁴H₂), 30.00 (C⁵H₂), 29.75 (C³H₂), 23.79 (C²H₂), 23.62 (C⁶H₂), 14.38 (CH₃). HRMS: m/z calcd for C₁₄H₃₁OS [M + H]: 247.2096; found: 247.2100. Anal. Calcd (%): C, 68.23; H, 12.27; S, 13.01. Found: C, 68.07; H, 12.30; S, 13.15. tert-Amyl Ethyl Sulfoxide (5a) Colorless oil. IR: ν_max = 2969, 2936, 2880, 1462, 1382, 1365, 1044, 1010, 972 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.75–2.65, 2.61–2.51 (2 m, total 2 H, SCH ₂Me), 1.77–1.66 (m, 1 H, MeCH ₂CMe₂), 1.63–1.52 (m, 1 H, MeCH ₂CMe₂), 1.368 (t, J  = 7.5  Hz, 3 H, SCH₂CH ₃), 1.227 (s, 3 H, SC(CH₃)₂), 1.182 (s, 3 H, SC(CH₃)₂), 1.008 (t, J =7.6  Hz, 3 H, CH ₃CH₂CMe₂). ¹³C NMR (125 MHz, СD₃OD): δ = 57.64 (SCMe₂), 39.17 (SCH₂Me), 30.01 (MeCH₂CMe₂), 19.71 and 19.41 (SC(CH₃)₂), 8.73 (SCH₂ CH₃), 8.15 (CH₃CH₂CMe₂). HRMS: m/z calcd for C₇H₁₇OS [M + H]: 149.1000; found: 149.1000. Anal. Calcd (%): C, 56.71; H, 10.88; S, 21.63. Found: C, 56.94; H, 10.79; S, 21.45. Diisobutyl Sulfoxide (6a) IR: ν_max = 2922, 2854, 1456, 1379, 1016 cm^–1. ¹H NMR (500 MHz, СD₃OD): δ = 2.74–2.69, 2.61–2.55 (2 m, 4 H, CH₂), 2.21–2.11 (m, 2 H, CH), 1.12–1.08 (m, 12 H, CH₃). ¹³C NMR (125 MHz, СD₃OD): δ = 62.41 (CH₂), 25.15 (CH), 23.06 (CH₃), 21.74 (CH₃). HRMS: m/z calcd for C₈H₁₉OS [M + H]: 163.1157; found: 163.1151. Anal. Calcd (%): C, 59.21; H, 11.18; S, 19.76. Found: C, 59.29; H, 11.32; S, 20.12. 3,5-Dimethyl-4-[(pentylsulfinyl)methyl]-1H-pyrazole (12a) White crystals, mp 87 °C. IR: ν_max = 2949, 2923, 2853, 1590, 1461, 1415, 1377, 1308, 1207, 1139, 1109, 1072, 1034, 1017, 1003, 949, 875, 835, 758, 729 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 12.206 (s, wide, 1 H, NH), 3.861 (d, J = 7.0  Hz, 1 H, SCH ₂-pyrazole), 3.719 (d, J = 7.0  Hz, 1 H, SCH ₂-pyrazole), 2.71–2.62 (m, 1 H, SCH ₂CH₂), 2.60–2.53 (m, 1 H, SCH ₂CH₂), 2.129 (s, 6 H, CH_3(pyrazole)), 1.72–1.55 (m, 2 H, SCH₂CH ₂), 1.43–1.25 (m, 4 H, CH₂), 0.872 (t, 3 H, CH₂CH ₃). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 128.23, 104.90 (SCH₂-pyrazole), 50.08, 46.52, 30.35, 26.73, 21.76, 21.70, 13.66, 10.66 (br, 2 Me). HRMS: m/z calcd for C₁₁H₂₁OS [M + H]: 229.1375; found: 229.1379. Anal. Calcd (%): C, 57.86; H, 8.83; N, 12.27; S, 14.04. Found: C, 57.91; H, 8.95; N, 12.28; S, 14.19.
• 18a Ulendeeva AD, Nikitina TS, Baeva LA, Spitikhin LV, Karachurina LT, Khisamutdinova RYu, Makara NS, Zarudii FS, Lyapina NK. Pharm. Chem. J. 2004; 38: 659
• 18b Ulendeeva AD, Baeva LA, Nikitina TS, Spitikhin LV, Vasil’eva EV, Lyapina NK. Pet. Chem. 2004; 44: 388
• 19a Tarsis E, Gromova A, Lim D, Zhou G, Coltart DM. Org. Lett. 2008; 10: 4819
• 19b Horhant D, Lamer A.-CL, Boustie J, Uriac P, Gouault N. Tetrahedron Lett. 2007; 48: 6031