Activation of hydrogen peroxide through hydrogen-bonding interaction with acidic alcohols: Epoxidation of alkenes in phenol

Organic Letters

Volumn 5, Issue 10, 2003, Pages 1777-1780

  Wahlen, Joos ^a   De Vos, Dirk E ^a   Jacobs, Pierre A ^a  

^a UNIVERSITY OF LEUVEN   (Belgium)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALKENE; HYDROGEN; HYDROGEN PEROXIDE; METAL; OXYGEN; PHENOL; SOLVENT;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL STRUCTURE; EPOXIDATION; HYDROGEN BOND; MOLECULAR INTERACTION; OXIDATION; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0141741202     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0344422     Document Type: Article

References (41)

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21. IV resulted in the immediate formation of a black precipitate.
22. 2. In one comparative example, phenol was used in the absence of As, but only a low yield was obtained. McMullen, C. H.; Fehskens, E. E.; Plotkin, J. S. U.S. Patent 4 410 715, 1983.
23. It is well-known that small amounts of phenolic compounds play a key role in the protection of living organisms and synthetic materials against oxidative damage. In such reactions, a phenol acts as a radical scavenger by hydrogen atom transfer to a peroxyl radical. For example, see: (a) Avila, D. V. ; Ingold, K. U.; Lusztyk, J.; Green, W. H.; Procopio, D. R. J. Am. Chem. Soc. 1995, 117, 2929-2930. (b) Wright, J. S.; Johnson, E. R.; DiLabio, G. A. J. Am. Chem. Soc. 2001, 123, 1173-1183.
24. It is well-known that small amounts of phenolic compounds play a key role in the protection of living organisms and synthetic materials against oxidative damage. In such reactions, a phenol acts as a radical scavenger by hydrogen atom transfer to a peroxyl radical. For example, see: (a) Avila, D. V. ; Ingold, K. U.; Lusztyk, J.; Green, W. H.; Procopio, D. R. J. Am. Chem. Soc. 1995, 117, 2929-2930. (b) Wright, J. S.; Johnson, E. R.; DiLabio, G. A. J. Am. Chem. Soc. 2001, 123, 1173-1183.
25. Reference radicals were generated by Fenton's reagent: (a) Harbour, J. R.; Chow, V.; Bolton, J. R. Can. J. Chem. 1974, 52, 3549-3553. (b) Janzen, E. G.; Nutter, D. E., Jr.; Davis, E. R.; Blackburn, B. J.; Poyer, J. L.; McCay, P. B. Can. J. Chem. 1978, 56, 2237-2242.
26. Reference radicals were generated by Fenton's reagent: (a) Harbour, J. R.; Chow, V.; Bolton, J. R. Can. J. Chem. 1974, 52, 3549-3553. (b) Janzen, E. G.; Nutter, D. E., Jr.; Davis, E. R.; Blackburn, B. J.; Poyer, J. L.; McCay, P. B. Can. J. Chem. 1978, 56, 2237-2242.
27. Presence of benzoquinone may induce some dioxirane-like chemistry. To disprove this possibility, various sets of control experiments were carried out. Details are shown in Supporting Information.
28. 3.
29. 2 to form reactive peroxy species.
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32. 1,2-Dichloroethane was used as a cosolvent to dissolve the high-melting phenols. Under these conditions, but in the absence of phenol, epoxidation hardly occurred (conversion was <3% after 24 h).
33. Similar cyclic hydrogen-bonded interactions of peroxides with alcohols have been proposed: (a) Dankleff, M. A. P.; Curci, R.; Edwards, J. O.; Pyun, H.-Y. J. Am. Chem. Soc. 1968, 90, 3209-3218. (b) Bruice, T. C.; Noar, J. B.; Ball, S. S.; Venkataram, U. V. J. Am. Chem. Soc. 1983, 105, 2452-2463. (c) Richardson, W. H. In The Chemistry of Functional Groups, Peroxides; Patai, S., Ed.; John Wiley & Sons: New York, 1983; Chapter 5. (d) Bach, R. D.; Su, M.-D.; Schlegel, H. B. J. Am. Chem. Soc. 1994, 116, 5379-5391.
34. Similar cyclic hydrogen-bonded interactions of peroxides with alcohols have been proposed: (a) Dankleff, M. A. P.; Curci, R.; Edwards, J. O.; Pyun, H.-Y. J. Am. Chem. Soc. 1968, 90, 3209-3218. (b) Bruice, T. C.; Noar, J. B.; Ball, S. S.; Venkataram, U. V. J. Am. Chem. Soc. 1983, 105, 2452-2463. (c) Richardson, W. H. In The Chemistry of Functional Groups, Peroxides; Patai, S., Ed.; John Wiley & Sons: New York, 1983; Chapter 5. (d) Bach, R. D.; Su, M.-D.; Schlegel, H. B. J. Am. Chem. Soc. 1994, 116, 5379-5391.
35. Similar cyclic hydrogen-bonded interactions of peroxides with alcohols have been proposed: (a) Dankleff, M. A. P.; Curci, R.; Edwards, J. O.; Pyun, H.-Y. J. Am. Chem. Soc. 1968, 90, 3209-3218. (b) Bruice, T. C.; Noar, J. B.; Ball, S. S.; Venkataram, U. V. J. Am. Chem. Soc. 1983, 105, 2452-2463. (c) Richardson, W. H. In The Chemistry of Functional Groups, Peroxides; Patai, S., Ed.; John Wiley & Sons: New York, 1983; Chapter 5. (d) Bach, R. D.; Su, M.-D.; Schlegel, H. B. J. Am. Chem. Soc. 1994, 116, 5379-5391.
36. Similar cyclic hydrogen-bonded interactions of peroxides with alcohols have been proposed: (a) Dankleff, M. A. P.; Curci, R.; Edwards, J. O.; Pyun, H.-Y. J. Am. Chem. Soc. 1968, 90, 3209-3218. (b) Bruice, T. C.; Noar, J. B.; Ball, S. S.; Venkataram, U. V. J. Am. Chem. Soc. 1983, 105, 2452-2463. (c) Richardson, W. H. In The Chemistry of Functional Groups, Peroxides; Patai, S., Ed.; John Wiley & Sons: New York, 1983; Chapter 5. (d) Bach, R. D.; Su, M.-D.; Schlegel, H. B. J. Am. Chem. Soc. 1994, 116, 5379-5391.
37. Epoxidation of cyclooctene using tert-butyl hydroperoxide as the oxidant at 60°C gave 20% conversion after 24 h.
38. 2 in other solvents (e.g., δ 176 ppm in methanol).
39. Reduction of charge separation in transition states by intramolecular hydrogen bonding and proton transfer is a generally accepted concept, e.g., the "butterfly" transition state in epoxidations mediated by typical peracids: (a) Bartlett, P. D. Rec. Chem. Prog. 1950, 11, 47-51. (b) Bach, R. D. ; Owensby, A. L.; Gonzalez, C.; Schlegel, H. B.; McDouall, J. J. W. J. Am. Chem. Soc. 1991, 113, 2338-2339.
40. Reduction of charge separation in transition states by intramolecular hydrogen bonding and proton transfer is a generally accepted concept, e.g., the "butterfly" transition state in epoxidations mediated by typical peracids: (a) Bartlett, P. D. Rec. Chem. Prog. 1950, 11, 47-51. (b) Bach, R. D. ; Owensby, A. L.; Gonzalez, C.; Schlegel, H. B.; McDouall, J. J. W. J. Am. Chem. Soc. 1991, 113, 2338-2339.
41. Chlorinated cosolvents, which are less coordinating, have a much less negative effect on the rate of epoxidation.