Reaction of highly methylated 2-methylenecycloalkyl hydroperoxides with FeSO4/CuCl2. Remarkably efficient 5-endo-trig or 6-endo-trig cyclization of the intermediate carbon radicals

Journal of Organic Chemistry

Volumn 64, Issue 11, 1999, Pages 4060-4063

  Nonami, Yuji ^a   Baran, Janusz ^b   Sosnicki, Jacek ^b   Mayr, Herbert ^c   Masuyama, Araki ^a   Nojima, Masatomo ^a  

^a OSAKA UNIVERSITY   (Japan)

^b WEST POMERANIAN UNIVERSITY OF TECHNOLOGY   (Poland)

^c UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

1,3,3,4,4,5,5 HEPTAMETHYL 2 METHYLENECYCLOPENTYL HYDROPEROXIDE; 2 METHYLENECYCLOALKYL HYDROPEROXIDE; COPPER CHLORIDE; FERROUS SULFATE; ORGANIC COMPOUND; UNCLASSIFIED DRUG;

ARTICLE; BIOTRANSFORMATION; CHEMICAL REACTION KINETICS; CYCLIZATION; METHYLATION; ORGANIC CHEMISTRY; PHOTOOXIDATION; REACTION ANALYSIS;

EID: 0033612224     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo990127a     Document Type: Article

References (31)

1. (a) Singlet Oxygen; Wasserman, H. H., Murray, R. W., Eds.; Academic Press: New York, 1979.
2. (b) Foote, C. S.; Clennan, E. L. In Active Oxygen in Chemistry; Foote, C. S., Valentine, J. S., A. Greenberg, A., Liebman, J. F., Eds.; Blackie Academic & Professional: London, 1995; Vol. 2.
3. Prein, M.; Adam, W. Angew. Chem., Int. Ed. Engl. 1996, 35, 477.
4. Adam, W.; Richter, M. J. Acc. Chem. Res. 1994, 27, 57 and references therein.
5. Adam, W.; Klug, P. Synthesis 1994, 557 and references therein.
6. (a) Dussault, P. H. In Active Oxygen in Chemistry; Foote, C. S., Valentine, J. S., Greenberg, A., Liebman, J. F., Eds.; Blackie Academic & Professional: London, 1995; Vol. 2.
7. (b) Curran, D. P. In Comprehensive Organic Chemistry; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol 4, p 823.
8. (c) McCullough, K. J.; Motomura, Y.; Masuyama, A.; Nojima, M. Chem. Commun. 1998, 1173 and references therein.
9. Bona fide examples of 5-endo cyclizations are even rarer than their 4-exo counterparts. (a) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim; 1996. (b) Mendenhall, G. D.; Protasiewicz, J. D.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 1718. (c) Ponaras, A. A.; Zaim, Ö. Tetrahedron Lett. 1993, 34, 2879. (d) Sato, T.; Machigashira, N.; Ishibashi, H.; Ikeda, M. Heterocycles 1992, 33, 139. (e) Cassayre, J.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron 1998, 54, 1029.
10. Bona fide examples of 5-endo cyclizations are even rarer than their 4-exo counterparts. (a) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim; 1996. (b) Mendenhall, G. D.; Protasiewicz, J. D.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 1718. (c) Ponaras, A. A.; Zaim, Ö. Tetrahedron Lett. 1993, 34, 2879. (d) Sato, T.; Machigashira, N.; Ishibashi, H.; Ikeda, M. Heterocycles 1992, 33, 139. (e) Cassayre, J.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron 1998, 54, 1029.
11. Bona fide examples of 5-endo cyclizations are even rarer than their 4-exo counterparts. (a) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim; 1996. (b) Mendenhall, G. D.; Protasiewicz, J. D.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 1718. (c) Ponaras, A. A.; Zaim, Ö. Tetrahedron Lett. 1993, 34, 2879. (d) Sato, T.; Machigashira, N.; Ishibashi, H.; Ikeda, M. Heterocycles 1992, 33, 139. (e) Cassayre, J.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron 1998, 54, 1029.
12. Bona fide examples of 5-endo cyclizations are even rarer than their 4-exo counterparts. (a) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim; 1996. (b) Mendenhall, G. D.; Protasiewicz, J. D.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 1718. (c) Ponaras, A. A.; Zaim, Ö. Tetrahedron Lett. 1993, 34, 2879. (d) Sato, T.; Machigashira, N.; Ishibashi, H.; Ikeda, M. Heterocycles 1992, 33, 139. (e) Cassayre, J.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron 1998, 54, 1029.
13. Bona fide examples of 5-endo cyclizations are even rarer than their 4-exo counterparts. (a) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim; 1996. (b) Mendenhall, G. D.; Protasiewicz, J. D.; Brown, C. E.; Ingold, K. U.; Lusztyk, J. J. Am. Chem. Soc. 1994, 116, 1718. (c) Ponaras, A. A.; Zaim, Ö. Tetrahedron Lett. 1993, 34, 2879. (d) Sato, T.; Machigashira, N.; Ishibashi, H.; Ikeda, M. Heterocycles 1992, 33, 139. (e) Cassayre, J.; Quiclet-Sire, B.; Saunier, J.-B.; Zard, S. Z. Tetrahedron 1998, 54, 1029.
14. The appropriate placement of activating groups can also be used to accelerate 6-endo cyclizations. (a) Beckwith, A. L.; Gream, G. E.; Struble, D. L. Aust. J. Chem. 1972, 25, 1081. (b) Wehle, D.; Schormann, N.; Fitjer, L. Chem. Ber. 1988, 121, 2171. (c) Satoh, T.; Itoh, M.; Yamakawa, K. Chem. Lett. 1987, 1949. See also: Handa, S.; Pattenden, G.; Li, W.-S. Chem. Commun. 1998, 311.
15. The appropriate placement of activating groups can also be used to accelerate 6-endo cyclizations. (a) Beckwith, A. L.; Gream, G. E.; Struble, D. L. Aust. J. Chem. 1972, 25, 1081. (b) Wehle, D.; Schormann, N.; Fitjer, L. Chem. Ber. 1988, 121, 2171. (c) Satoh, T.; Itoh, M.; Yamakawa, K. Chem. Lett. 1987, 1949. See also: Handa, S.; Pattenden, G.; Li, W.-S. Chem. Commun. 1998, 311.
16. The appropriate placement of activating groups can also be used to accelerate 6-endo cyclizations. (a) Beckwith, A. L.; Gream, G. E.; Struble, D. L. Aust. J. Chem. 1972, 25, 1081. (b) Wehle, D.; Schormann, N.; Fitjer, L. Chem. Ber. 1988, 121, 2171. (c) Satoh, T.; Itoh, M.; Yamakawa, K. Chem. Lett. 1987, 1949. See also: Handa, S.; Pattenden, G.; Li, W.-S. Chem. Commun. 1998, 311.
17. The appropriate placement of activating groups can also be used to accelerate 6-endo cyclizations. (a) Beckwith, A. L.; Gream, G. E.; Struble, D. L. Aust. J. Chem. 1972, 25, 1081. (b) Wehle, D.; Schormann, N.; Fitjer, L. Chem. Ber. 1988, 121, 2171. (c) Satoh, T.; Itoh, M.; Yamakawa, K. Chem. Lett. 1987, 1949. See also: Handa, S.; Pattenden, G.; Li, W.-S. Chem. Commun. 1998, 311.
18. 3, followed by column chromatography on silica gel, afforded (2,3,3,4,4,5,5-heptamethyl-1-cyclopentenyl)methyl hydroperoxide (5a) in 25% yield, together with unidentified decomposition products. In this connection, allylic hydroperoxides are known to be labile toward acid catalysts. Schenck, G. O.; Schulte-Elte, K.-H. Liebigs Ann. Chem. 1958, 618, 185.
19. (a) Lowe, J. R.; Porter, N. A. J. Am. Chem. Soc. 1997, 119, 11534.
20. (b) Dussault, P. H.; Woller, K. R. J. Am. Chem. Soc. 1997, 119, 3824.
21. (c) Dang, H.-S.; Davies, A. G.; Davison, I. G. E.; Schiesser, C. H. J. Org. Chem. 1990, 55, 1432.
22. (d) Schenck, G. O.; Neumüller, O.-A.; Eisfeld, W. Liebigs Ann. Chem. 1958, 618, 202.
23. Orfanopoulos, M.; Stratakis, M.; Elemes, Y. Jensen, F. J. Am. Chem. Soc. 1991, 113, 3180. See also: (a) Linker, T.; Fröhlich, L. J. Am. Chem. Soc. 1995, 117, 2694.
24. Orfanopoulos, M.; Stratakis, M.; Elemes, Y. Jensen, F. J. Am. Chem. Soc. 1991, 113, 3180. See also: (a) Linker, T.; Fröhlich, L. J. Am. Chem. Soc. 1995, 117, 2694.
25. (b) Davis, K. M.; Carpenter, B. K. J. Org. Chem. 1996, 61, 4617.
26. (c) Clennan, E. L.; Chen, X.; Koola, J. J. J. Am. Chem. Soc. 1990, 112, 5193.
27. β-Scission is a well-established reaction of many alkoxyl radicals. The extent to which β-scission occurs is determined by a number of factors, one of which is the stability of the organic radical generated: Labeque, R.; Marnett, L. J. J. Am. Chem. Soc. 1987, 109, 2828.
28. Fenical, W.; Kearns, D. R.; Radlick, P. J. Am. Chem. Soc. 1969, 91, 3396.
29. 2 gives 1-chlorocyclohexyl methyl ketone in 55% yield. Masuyama, A.; Sugawara, T.; Nojima, M. Unpublished result.
30. Klein, H.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1981, 20, 1027.
31. Mayr, H.; Klein, H.; Sippel, E. Chem. Ber. 1983, 116, 3624.