Surface-mediated reactions. 8. Oxidation of sulfides and sulfoxides with tert-butyl hydroperoxide and OXONE

Journal of the American Chemical Society

Volumn 122, Issue 18, 2000, Pages 4280-4285

  Kropp, Paul J ^a   Breton, Gary W ^a   Fields, John D ^a   Tung, Jesse C ^a   Loomis, Brian R ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALUMINUM OXIDE; INORGANIC SALT; OXIDIZING AGENT; SILANE DERIVATIVE; SILICA GEL; SULFIDE; SULFOXIDE; TERT BUTYL HYDROPEROXIDE;

ADSORPTION; ARTICLE; OXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE; SURFACE PROPERTY;

EID: 0034630941     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9940569     Document Type: Article

References (41)

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2. For reviews, see: (a) Preparative Chemistry Using Supported Reagents; Laszlo, P., Ed.; Academic: San Diego, 1987. (b) Solid Supports and Catalysts in Organic Synthesis; Smith, K., Ed.; Ellis Horwood: New York, 1992. (c) Clark, J. H. Catalysis of Organic Reactions by Supported Inorganic Reagents; VCH: New York, 1994. (d) Kabalka, G. W.; Pagni, R. M. Tetrahedron 1997, 53, 7999-8605.
3. For reviews, see: (a) Preparative Chemistry Using Supported Reagents; Laszlo, P., Ed.; Academic: San Diego, 1987. (b) Solid Supports and Catalysts in Organic Synthesis; Smith, K., Ed.; Ellis Horwood: New York, 1992. (c) Clark, J. H. Catalysis of Organic Reactions by Supported Inorganic Reagents; VCH: New York, 1994. (d) Kabalka, G. W.; Pagni, R. M. Tetrahedron 1997, 53, 7999-8605.
4. For reviews, see: (a) Preparative Chemistry Using Supported Reagents; Laszlo, P., Ed.; Academic: San Diego, 1987. (b) Solid Supports and Catalysts in Organic Synthesis; Smith, K., Ed.; Ellis Horwood: New York, 1992. (c) Clark, J. H. Catalysis of Organic Reactions by Supported Inorganic Reagents; VCH: New York, 1994. (d) Kabalka, G. W.; Pagni, R. M. Tetrahedron 1997, 53, 7999-8605.
5. For reviews, see: (a) Preparative Chemistry Using Supported Reagents; Laszlo, P., Ed.; Academic: San Diego, 1987. (b) Solid Supports and Catalysts in Organic Synthesis; Smith, K., Ed.; Ellis Horwood: New York, 1992. (c) Clark, J. H. Catalysis of Organic Reactions by Supported Inorganic Reagents; VCH: New York, 1994. (d) Kabalka, G. W.; Pagni, R. M. Tetrahedron 1997, 53, 7999-8605.
6. For a preliminary report of a portion of these studies, see: Breton, G. W.; Fields, J. D.; Kropp, P. J. Tetrahedron Lett. 1995, 56, 3825-3828.
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8. 3COH, is easily removed from reaction mixtures by distillation or rotary evaporation, obviating the need for aqueous workup as required for the traditionally used peroxyacid oxidants. This is particularly useful since the products of many oxidations are water soluble.
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10. To provide qualitative rate data, oxidations were terminated prior to total conversion. For preparative purposes, complete oxidation can be effected by using longer reaction times or employing a small excess of oxidant.
11. 3COOH afforded slower oxidation. Tung, J. C. Unpublished results.
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13. See, for example: (a) Kropp, P. J.; Daus, K. A.; Tubergen, M. W.; Kepler, K. D.; Wilson, V. P.; Craig, S. L.; Baillargeon, M. M.; Breton, G. W. J. Am. Chem. Soc. 1993, 115, 3071-3079. (b) Kropp, P. J.; Crawford, S. D. J. Org. Chem. 1994, 59, 3102-3112. (c) Kropp, P. J.; Breton, G. W.; Craig, S. L.; Crawford, S. D.; Durland, W. F., Jr.; Jones, J. E., III; Raleigh, J. S. J. Org. Chem. 1995, 60, 4146-4152.
14. See, for example: (a) Kropp, P. J.; Daus, K. A.; Tubergen, M. W.; Kepler, K. D.; Wilson, V. P.; Craig, S. L.; Baillargeon, M. M.; Breton, G. W. J. Am. Chem. Soc. 1993, 115, 3071-3079. (b) Kropp, P. J.; Crawford, S. D. J. Org. Chem. 1994, 59, 3102-3112. (c) Kropp, P. J.; Breton, G. W.; Craig, S. L.; Crawford, S. D.; Durland, W. F., Jr.; Jones, J. E., III; Raleigh, J. S. J. Org. Chem. 1995, 60, 4146-4152.
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19. We have found that the need to add water varies from batch to batch of OXONE, which is hygroscopic. Thus the reagent might better be described as, "moist" OXONE supported on alumina or silica gel.
20. 3COOH/alumina or OXONE over either silica gel or alumina gave inferior results.
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23. For descriptions of current models for the surfaces of alumina and silica gel, see: (a) Knözinger, H. In The Hydrogen Bond. III. Dynamics, Thermodynamics and Special Systems; Schuster, P., Zundel, G., Sandorfy, C., Eds.; North-Holland: Amsterdam, 1976; Chapter 27. (b) Dufour, P.; Houtman, C.; Santini, C. C.; Nédez, C.; Basset, J. M.; Hsu, L. Y.; Shore, S. G. J. Am. Chem. Soc. 1992, 114, 4248-4257.
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26. See, however, ref 9.
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29. By convention, the mechanisms of oxidation reactions are characterized in terms of the mode of action of the oxidant.
30. so values >0.5 and electrophilic oxidants values <0.5.
31. 17 However, since sulfone 3a is less strongly adsorbed, it will equilibrate with remaining sulfoxide 2b, permitting further oxidation.
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33. See: (a) Leffler, J. E.; Miller, D. W. J. Am. Chem. Soc. 1977, 99, 480-483. (b) Rebek, J.; McCready, R. Tetrahedron Lett. 1979, 45, 4337-4338.
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36. The role of water in facilitating reactions involving solid reagents has been attributed to breakup of the crystal lattice: (a) Carpino, L. A.; Sau, A. C. J. Chem. Soc., Chem. Commun. 1979, 514. (b) Tanaka, M.; Koyanagi, M. Synthesis 1981, 973-975. (c) Hirano, M.; Yakabe, S.; Monobe, H.; Morimoto, T. Can. J. Chem. 1977, 75, 1905-1912.
37. The role of water in facilitating reactions involving solid reagents has been attributed to breakup of the crystal lattice: (a) Carpino, L. A.; Sau, A. C. J. Chem. Soc., Chem. Commun. 1979, 514. (b) Tanaka, M.; Koyanagi, M. Synthesis 1981, 973-975. (c) Hirano, M.; Yakabe, S.; Monobe, H.; Morimoto, T. Can. J. Chem. 1977, 75, 1905-1912.
38. The role of water in facilitating reactions involving solid reagents has been attributed to breakup of the crystal lattice: (a) Carpino, L. A.; Sau, A. C. J. Chem. Soc., Chem. Commun. 1979, 514. (b) Tanaka, M.; Koyanagi, M. Synthesis 1981, 973-975. (c) Hirano, M.; Yakabe, S.; Monobe, H.; Morimoto, T. Can. J. Chem. 1977, 75, 1905-1912.
39. Alternatively, adsorption might be viewed as involving OXONE and adsorbed water at the associated sites.
40. The need for this step varied from batch to batch of OXONE.
41. Microwave heating was conducted using a commercial 500-W Little Litton oven.