endo/exo Isomerism in Norcarane and 2-Norcaranol Hydrotrioxides (ROOOH)

Journal of Organic Chemistry

Volumn 68, Issue 23, 2003, Pages 9129-9131

  Eržen, Evgen ^a   Cerkovnik, Janez ^a   Plesničar, Božo ^a  

^a UNIVERSITY OF LJUBLJANA   (Slovenia)

Author keywords

[No Author keywords available]

Indexed keywords

PRIMARY DECOMPOSITION PRODUCTS;

DECOMPOSITION; ISOMERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OZONIZATION;

ORGANIC COMPOUNDS;

2 NORCARANOL HYDROTRIOXIDE DERIVATIVE; HYDROGEN; OXIDE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; DECOMPOSITION; ISOMERISM; OZONATION; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0242576113     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo035154m     Document Type: Article

References (34)

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2. (b) de Meijere, A.; Wolf, F. In Organische Peroxo-Verbindungen; Kropf, H., Ed.; Houben-Weyl Methoden der Organischen Chemie, Vol. E13; George Thieme Verlag: Stuttgart and New York, 1988; pp 971-990.
3. (a) Plesničar, B.; Cerkovnik, J.; Tekavec, T.; Koller, J. J. Am. Chem. Soc. 1998, 120, 8005.
4. (b) Plesničar, B.; Cerkovnik, J.; Tekavec, T.; Koller, J. Chem. Eur. J. 2000, 6, 809
5. (c) Wu, A.; Cremer, D.; Plesničar, B. J. Am. Chem. Soc, 2003, 125, 9395 and references therein.
6. (a) Wentworth, P., Jr.; Jones, L. H.; Wentworth, A. D.; Zhu, X.; Larsen, N. A.; Wilson, I. A.; Xu, X.; Goddard, W. A., III; Janda, K. D.; Eschenmoser, A.; Lerner, R. A. Science 2001, 293, 1806.
7. (b) Xu, X.; Muller, R. P.; Goddard, W. A., III. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 3376.
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9. (d) Wentworth, P., Jr.; Wentworth, A. D.; Zhu, X.; Wilson, I. A.; Janda, K. D.; Eschenmoser, A.; Lerner, R. A. Proc. Natl. Acad. Sci. U.S.A. 2003, 100, 1490.
10. Xu, X.; Goddard, W. A., III. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 15308 and references therein.
11. (a) Cerkovnik, J.; Eržen, E.; Koller, J.; Plesničar, B. J. Am. Chem. Soc. 2002, 124, 404.
12. (b) For the previous studies on the involvement of hydrotrioxides in the ozonation of cumene and some other saturated hydrocarbons, see: Pryor, W. A.; Ohto, N.; Church, D. F. J. Am. Chem. Soc. 1983, 105, 3614. Giamalva, D. H.; Church, D. F.; Pryor, W. A. J. Org. Chem. 1988, 53, 3429.
13. (b) For the previous studies on the involvement of hydrotrioxides in the ozonation of cumene and some other saturated hydrocarbons, see: Pryor, W. A.; Ohto, N.; Church, D. F. J. Am. Chem. Soc. 1983, 105, 3614. Giamalva, D. H.; Church, D. F.; Pryor, W. A. J. Org. Chem. 1988, 53, 3429.
14. Zarth, M.; de Meijere, A. Chem. Ber. 1985, 118, 2429.
15. Norcarane was prepared by using the Simmons-Smith reaction: Friedrich, E. C.; Lunetta, S. E.; Lewis, E. J. J. Org. Chem. 1988, 54, 2388.
16. .) were detected in the reaction mixtures.
17. (b) Pryor et al. have suggested that transition states for the ozonation of C-H bonds in saturated systems might have contributions ranging from radical to ionic resonance forms, depending on the substrate and the experimental conditions used.5b See also: Giamalva, D. H.; Church, D. F.; Pryor, W. A. J. Am. Chem. Soc. 1986, 108, 7678.
18. (c) For use of norcarane as a probe for radicals in cytochrome P450 catalyzed hydroxylation reactions, see: Auclair, K.; Hu, Z.; Little, D. M.; Ortiz de Montellano, P. R.; Groves, J. T. J. Am. Chem. Soc. 2002, 124, 6020. Newcomb, M.; Shen, R.; Lu, Y.; Coon, M. J.; Hollenberg, P. F.; Koop, D. A.; Lippard, S. J. J. Am. Chem. Soc. 2002, 124, 6879.
19. (c) For use of norcarane as a probe for radicals in cytochrome P450 catalyzed hydroxylation reactions, see: Auclair, K.; Hu, Z.; Little, D. M.; Ortiz de Montellano, P. R.; Groves, J. T. J. Am. Chem. Soc. 2002, 124, 6020. Newcomb, M.; Shen, R.; Lu, Y.; Coon, M. J.; Hollenberg, P. F.; Koop, D. A.; Lippard, S. J. J. Am. Chem. Soc. 2002, 124, 6879.
20. GC-MS analysis of the reaction mixture after the decomposition of 2a and 2b gave the same ratio of isomeric endo- and exo-2-norcaranol (3a:3b = 1:0.06), which are, in addition to 2-norcaranone (6), the main decomposition products (54 mol %).
21. + = 128). For NMR spectroscopic data of 5a and 5b, see Table 1.
22. (b) Davies, A. G.; Foster, R. V.; White, J. M. J. Chem. Soc. 1953, 1541.
23. (c) For a recent review on alkyl hydroperoxides (ROOH), see: Porter, N. A. In Organic Peroxides; Ando, W., Ed.; Wiley: New York, 1992; pp 101-156.
24. 17O NMR spectroscopy.2 For a complete study of the ozonation of hydrazines, see: Plesničar, B.; Tuttle, T.; Cerkovnik, J.; Koller, J.; Cremer, D. J. Am. Chem. Soc. 2003, 125, 11553.
25. The preferred formation of the "endo" hydrotrioxide 3a might be due to the interaction of the electrophilic ozone with the "nucleophilic" cyclopropane ring of 1. (de Meijere, A. Angew. Chem., Int. Ed. Engl. 1979, 18, 809. The Chemistry of the Cyclopropyl Group; Rappoport, Z., Ed.; Wiley: Chichester, 1995; Part II.)
26. The preferred formation of the "endo" hydrotrioxide 3a might be due to the interaction of the electrophilic ozone with the "nucleophilic" cyclopropane ring of 1. (de Meijere, A. Angew. Chem., Int. Ed. Engl. 1979, 18, 809. The Chemistry of the Cyclopropyl Group; Rappoport, Z., Ed.; Wiley: Chichester, 1995; Part II.)
27. (a) endo-2-Norcaranol (3a) was prepared by stereoselective magnesium-promoted cyclopropanation of 2-cyclohexenol. Bolm, C.; Pupowicz, D. Tetrahedron Lett. 1997, 38, 7349.
28. (b) 2-Norcaranol (3) was prepared as a mixture of 3a and 3b from LAH reduction of 2-norcaranone (6). For preparation of 6, see: Dauben, E. G.; Berezin, G. H. J. Am. Chem. Soc. 1963, 85, 468.
29. 1H NMR (-60 °C). It should be pointed out that an excess of ozone (relative to 1) was used in all experiments.
30. Molar ratio HOOOH, 4a:4b = 1.0:0.20:0.16.
31. (a) Norcarane hydrotrioxides (2a, 2b) decomposed to norcaranols 3a and 3b and norcaranone (6), whereas norcaranol hydrotrioxides (4a, 4b) yielded 6 as the end decomposition product. Oxygen and hydrogen peroxide were also detected among the decomposition products.
32. (b) It should be pointed out that water was always present in the ozonized solutions of norcarane and 2-nocaranols, most likely due to the reaction of ozone with the hydrotrioxides 2a, 2b, 4a, 4b, HOOOH, and HOOH.2a,b,4
33. (c) For the proposed mechanism of the decomposition of the hydrotrioxides of saturated hydrocarbons, alcohols, and HOOOH, see refs 2, 4, 5, and 11.
34. The hydrotrioxides 4a and 4b are more stable than hydrotrioxides 2a and 2b, most probably because of a possibility of intramolecular hydrogen bonding in the former. See ref 2c.