H-abstraction prevails over α-cleavage in the solution and solid state photochemistry of cis-2,6-di(1-cyclohexenyl)cyclohexanone

Tetrahedron Letters

Volumn 44, Issue 32, 2003, Pages 6133-6136

  Mortko, Christopher J ^a   Dang, Hung ^a   Campos, Luis M ^a   García Garibay, Miguel A ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2,6 BIS(1 CYCLOHEXENYL)CYCLOHEXANONE; ALLYL COMPOUND; CARBONYL DERIVATIVE; CYCLOHEXANONE DERIVATIVE; HYDROGEN; METHANE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHROMATOPHORE; CIS ISOMER; PHOTOCHEMISTRY; PHOTOREACTIVITY; SOLID STATE; X RAY DIFFRACTION;

EID: 0037967855     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(03)01450-3     Document Type: Article

References (26)

1. Weiss D. Org. Photochem. 5:1981;347-420.
2. Campos L.M., Dang H., Ng D., Yang Z., Martinez H.L., Garcia-Garibay M.A. J. Org. Chem. 67:2002;3749-3754.
3. 2-H: Parkinson C.J., Mayer P.M., Radom L. J. Chem. Soc., Perkin Trans. 2. 1999;2305-2313.
4. Choi T., Cizmeciyan D., Khan S.I., Garcia-Garibay M.A. J. Am. Chem. Soc. 118:1995;12893-12894.
5. Choi T., Peterfy K., Khan S.I., Garcia-Garibay M.A. J. Am. Chem. Soc. 119:1996;12477-12478.
6. Peterfy K., Garcia-Garibay M.A. J. Am. Chem. Soc. 120:1998;4540-4541.
7. Yang Z., Ng D., Garcia-Garibay M.A. J. Org. Chem. 66:2001;4468-4475.
8. Yang Z., Garcia-Garibay M.A. Org. Lett. 2:2000;1963-1965.
9. Ellison, M. E., M.S. Thesis, University of California, Los Angeles, 2003.
10. Ng D., Yang Z., Garcia-Garibay M.A. Tetrahedron Lett. 43:2002;7063-7066.
11. Brocks J.J., Beckhaus H.-D., Beckwith A.L.J., Ruchardt C. J. Org. Chem. 63:1998;1935-1943.
12. Houk K.N. Chem. Rev. 76:1976;1-70.
13. For an excellent review of photoinduced H-atom abstraction in carbonyl compounds and a compelling suggestion to name the formation of cyclobutanols after Professor N.C. Yang, please see: Wagner P.J., Park B.-S. Org. Photochem. 11:1991;227-366.
14. In addition to cyclobutanol formation, 1,4-biradicals formed by γ-hydrogen abstraction can also cleave to give enol and alkene fragments. Cleavage is not observed in the case of β,γ-unsaturated carbonyls as the formation of ketenes is unfavorable.
15. Bell T.W., Vargas J.R., Crispino G.A. J. Org. Chem. 54:1989;1978-1987.
16. This result is in agreement with previous reports on 2-(1-cyclohexenyl)-cyclohexanone: (a) Cookson, R. C.; Rogers, N. R. J. Chem. Soc., Chem. Commun. 1972, 13, 809-810; (b) Cookson, R. C.; Rogers, N. R. J. Chem. Soc., Perkin Trans. 1. 1974, 10, 1037-1043.
17. This result is in agreement with previous reports on 2-(1-cyclohexenyl)-cyclohexanone: (a) Cookson, R. C.; Rogers, N. R. J. Chem. Soc., Chem. Commun. 1972, 13, 809-810; (b) Cookson, R. C.; Rogers, N. R. J. Chem. Soc., Perkin Trans. 1. 1974, 10, 1037-1043.
18. + 258.1984, obsd 258.1984.
19. Vedejs E., Little J. J. Am. Chem. Soc. 124:2002;748-749.
20. Isotope effects in H-transfer reactions are known to vary widely. Please see: Garcia-Garibay M.A., Gamarnik A., Bise R., Jenks W.S. J. Am. Chem. Soc. 117:1995;10264-10275.
21. Gunther H. NMR Spectroscopy. Basic Principles, Concepts, and Applications in Chemistry. 2nd ed: 1995;124 John Wiley & Sons, New York.
22. Ihmels H., Scheffer J.R. Tetrahedron. 55:1999;885-907.
23. Scheffer J.R. Desiraju G.R. Solid State Organic Chemistry. 1987;1-45 VCH, Amsterdam.
24. 2 (all data)=0.1377.
25. Salem L., Leforestier C., Segal G., Wetmore R. J. Am. Chem. Soc. 97:1975;479-487.
26. Cohen M.D. Angew. Chem., Int. Ed. Engl. 14:1975;386-393.