Cyclization of enediyne radical cations through chemical, photochemical, and electrochemical oxidation: The role of state symmetry

Journal of Organic Chemistry

Volumn 61, Issue 6, 1996, Pages 2247-2250

  Ramkumar, Dhruva ^a   Kalpana, Mahadevan ^a   Varghese, Babu ^a   Sankararaman, Sethuraman ^a   Jagadeesh, Mavinahalli N ^b   Chandrasekhar, Jayaraman ^b  

^a INDIAN INSTITUTE OF TECHNOLOGY MADRAS   (India)

^b INDIAN INSTITUTE OF SCIENCE   (India)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000655212     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo951524y     Document Type: Article

References (25)

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3. Nicolaou, K. C.; Dai, W.-M.; Tsay, S.-C.; Estevez, V. A.; Wrasidlo, W. Science 1992, 256, 1172.
4. Nicolaou, K. C.; Zuccarello, G.; Riemer, C.; Estevez, V. A.; Dai, W.-M. J. Am. Chem. Soc. 1992, 114, 7360.
5. Nicolaou, K. C.; Liu, A.; Zeng, Z.; McComb, S. J. Am. Chem. Soc. 1992, 114, 9276.
6. Muller, E.; Zountsas, G. Tetrahedron Lett. 1970, 52, 4531.
7. Konig, B.; Schofield, E.; Bubenitschek, P.; Jones, P. G. J. Org. Chem. 1994, 59, 7142.
8. Turro, N. J.; Evenzahav, A.; Nicolaou, K. C. Tetrahedron Lett. 1994, 35, 8089.
9. Wender, P. A.; Zercher, C. K.; Beckham, S.; Haubold, E.-M. J. Org. Chem. 1993, 58, 5867.
10. Zhou, Q.; Carroll, P. J.; Swager, T. M. J. Org. Chem. 1994, 59, 1294.
11. Bradshaw, J. D.; Solooki, D.; Tessier, C. A.; Youngs, W. J. J. Am. Chem. Soc. 1994, 116, 3177.
12. 3CN, E(S) = 2.8 eV, t(S) = 2.9 ns. Miranda, M. A.; Garcia, H. Chem. Rev. 1994, 94, 1063.
13. For the mechanism of photonitration of arenes with TNM see Sankararaman, S.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2 1991, 1, 165 and references cited therein. Further details of the photochemistry of enediyne-TNM system will be published separately.
14. Barton, D. H. R.; Leclerc, G.; Magnus, P. D.; Menzies, I. D. J. Chem. Soc., Chem. Commun. 1972, 447.
15. 9
16. Jones, G. II; Becker, W. G. J. Am. Chem. Soc. 1983, 105, 1276.
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18. Takahashi, Y; Sankararaman, S; Kochi, J. K. J. Am. Chem. Soc. 1989, 111, 2954.
19. Stewart, J. J. P. J. Comput. Aided Des. 1990, 4, 1.
20. Spin-projected Moller-Plesset theory is known to be more reliable in estimating energetics of species with varying degrees of contamination; see, Schlegel, H. B. J. Phys. Chem. 1988, 92, 3075.
21. Sosa, C.; Schlegel, H. B. J. Am. Chem. Soc. 1987, 109, 4193.
22. Calculations were carried out using the Gaussian 92 series of programs (Revision E.3): Frisch, M. J.; Trucks, G. W.; Head-Gordon, M; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J, J. P.; Pople, J. A., Gaussian, Inc., Pittsburgh, PA, 1992.
23. The computed AM1 heats of formation (kcal/mol) and ab initio total energies (UHF/3-21G, PUHF/6-31G*, and PMP2/6-31G* in hartree) of radical cations, respectively, are the following: enediyne, 320.2, (227.82730, 229.12994, 229.80966); 1,4-dehydrobenzene, 341.5, (227.81961, 229.07806, 229.82352); 3,6-dehydrofulvene (5π), 363.1, (227.79831, 229.15994, 229.77390); 3,6-dehydrofulvene (6π), 388.5, (227.77629, 229.10135, 229.74095); transition state between enediyne and 3,6-dehydrofulvene (5π), 377.9, (227.74429, 229.02437, 229.74796).
24. Whitlock, H. W. Jr; Sandvick, P. E; Overman, L. E; Reichardt, P. B. J. Org. Chem. 1969, 34, 879.
25. The author has deposited atomic coordinates for this structure with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.