Bulletin of the Korean Chemical Society

  • 제17권7호
  • /
  • Pages.625-630
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  • 1996
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Catalytic Oxygenation of Alkenes and Alkanes by Oxygen Donors Catalyzed by Cobalt-Substituted Polyoxotungstate

  • 발행 : 1996.07.20
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초록

The cobalt-substituted polyoxotungstate [(CoPW11O39)5-] has been used as a catalyst in olefin epoxidation and alkane hydroxylation reactions. The epoxidation of olefins by iodosylbenzene in CH3CN yielded epoxides predominantly with trace amounts of allylic oxidation products. cis-Stilbene was streoselectively oxidized to cis-stilbene oxide with small amounts of trans-stilbene oxide and benzaldehyde formation. The epoxidation of carbamazepine (CBZ) by potassium monopersulfate in aqueous solution gave the corresponding CBZ 10,11-oxide product. Other transition metal-substituted polyoxotungstates (M=Mn2+, Fe2+, Ni2+, and Cu2+) were inactive in the CBZ epoxidation reaction. The cobalt-substituted polyoxotungstate also catalyzed the oxidation of alkanes with m-chloroperbenzoic acid to give the corresponding alcohols and ketones. The presence of CH2Br2 in the hydroxylation of cyclohexane afforded the formation of bromocyclohexane, suggesting the participation of cyclohexyl radical. In the 18O-labeled water experiment, there was no incorporation of 18O into the cyclohexanol product when the hydroxylation of cyclohexane by MCPBA was carried out in the presence of H218O. Some mechanistic aspects are discussed as well.

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참고문헌

  1. The Activation of Dioxygen and Homogeneous Catalytic Oxidation Barton, E. H.(ed.);Martell, A. E.(ed.);Sawyer, D. T.(ed.)
  2. Catalytic Oxidations with Hydrogen Peroxide as Oxidant Strukul, G.(ed.)
  3. Metal-Catalyzed Oxidations of Organic Compounds Sheldon, R. A.(ed.);Kochi, J. K.(ed.)
  4. Metalloporphyrins Catalyzed Oxidations Montanari, F.(ed.);Casella, L.(ed.)
  5. Chem. Rev. v.92 Meunier, B.
  6. Science v.264 Grinstaff, M. W.;Hill, M. G.;Labinger, J. A.;Gray, H. B.
  7. Inorg. Chem. v.26 Traylor, T. G.;Tsuchiya, S.
  8. J. Am. Chem. Soc. v.117 Neumann, R.;Gara, M.
  9. J. Am. Chem. Soc. v.116 Neumann, R.;Gara, M.
  10. J. Am. Chem. Soc. v.115 Khenkin, A. M.;Hill, C. L.
  11. J. Am. Chem. Soc. v.115 Hou, Y.;Hill, C. L.
  12. J. Am. Chem. Soc. v.114 Rong, C.;Pope, M. T.
  13. J. Am. Chem. Soc. v.113 Mansuy, D.;Bartoli, J.-F.;Battioni, P.;Lyon, D. K.;Finke, R. G.
  14. J. Am. Chem. Soc. v.108 Hill, C. L.;Brown, R. B., Jr.
  15. J. Am. Chem. Soc. v.112 Neumann, R.;Abu-Gnim, C.
  16. Dioxygen Activation and Homogeneous Catalytic Oxidation Hill, C. L.;Renneke, R. F.;Faraj, M.;Simandi, L. I.(ed.)
  17. J. Am. Chem. Soc. v.117 Duncan, D. C.;Chambers, R. C.;Hecht, E.;Hill, C. L.
  18. J. Org. Chem. v.58 Hamamoto, M.;Nakayama, K.;Nishiyama, Y.;Ishii, Y.
  19. The Activation of Dioxygen and Homogeneous Catalytic Oxidation Valentine, J. S.;Nam, W.;Ho, R. Y. N.;Barton, E. H.(ed.);Martell, A. E.(ed.);Sawyer, D. T.(ed.)
  20. J. Am. Chem. Soc. v.105 Groves, J. T.;Nemo, T. E.
  21. J. Chem. Soc., Chem. Commun. Suslick, K. S.;Cook, B. R.
  22. Bull. Korean Chem. Soc. v.15 Nam, W.;Baek, S. J.;Liao, K. I.;Valentine, J. S.
  23. Inorg. Chem. v.23 VanAtta, R. B.;Franklin, C. C.;Valentine, J. S.
  24. J. Am. Chem. Soc. v.112 Nam, W.;Valnetine, J. S.
  25. J. Am. Chem. Soc. v.112 Yang, Y.;Diederich, F.;Valentine, J. S.
  26. J. Am. Chem. Soc. v.113 Yang, Y.;Diederich, F.;Valentine, J. S.
  27. J. Am. Chem. Soc. v.1117 Sam, J. W.;Tang, X.-J.;Magliozzo, R. S.;Peisach, J.
  28. Inorg. Chem. v.28 Magliozzo, R. S.;Peisach, J.
  29. Tetrahedron Lett. v.26 Moriarty, R. M.;Penmasta, R.;Prakash, I.
  30. Bull. Korean Chem. Soc. v.16 Nam, W.;Hwang, W.;Baek, S. J.;Sohn, B. C.
  31. Bull. Korean Chem. Soc. Nam, W.;Hwang, W.;Ahn, J. M.;Yi, S.-Y.;Jhon, G.-J.
  32. J. Am. Chem. Soc. v.115 Sorokin, A.;Robert, A.;Meunier, B.
  33. New J. Chem. v.16 Meunier, B.
  34. J. Am. Chem. Soc. v.116 Sam, J. W.;Tang, X.-J.;Peisach, J.
  35. J. Am. Chem. Soc. v.113 Nam, W.;Ho, R.;Valentine, J. S.
  36. Activation and Functionalization of Alkanes Barton, D. H. R.;Ozbalik, N.;Hill, C. L.(ed.)
  37. New J. Chem. v.13 Barton, D. H. R.;Halley, F.;Ozbalik, N.;Young, E.;Balavoine, G.;Gref, A.;Boivin, J.
  38. J. Am. Chem. Soc. v.115 Nam, W.;Valentine, J. S.
  39. J. Am. Chem. Soc. v.116 Bernadou, J.;Fabiano, A.-S.;Robert, A.;Meunier, B.
  40. J. Am. Chem. Soc. v.115 Leising, R. A.;Kim, J.;Perez, M. A.;Que, L., Jr.
  41. Inorg. Chem. v.29 Leising, R. A.;Norman, R. E.;Que, L., Jr.
  42. J. Am. Chem. Soc. v.105 Smegal, J. A.;Hill, C. L.
  43. J. Chem. Soc., Chem. Commun. Faraj, M.;Hill, C. L.
  44. Ph.D. dissertation, UCLA VanAtta, R.
  45. J. Am. Chem. Soc. v.105 Brevard, C.;Schimpf, R.;Tourne, G.;Tourne, C. M.