Synthesis and photoreaction of tricyclo[5.2.2.0 ^2,6]undecanes in the excited singlet (¹S  ) state: a novel and stereospecific route to protoilludanoids

Abstract

A novel and general approach to the synthesis of functionalised protoilludane skeletons having fusedfour-, six- and five-membered rings is described. A photochemical sigmatropic 1,3-acyl shift in endo-tricyclo[5.2.2.0 ^2,6]undecanes having a β,γ-unsaturated carbonyl chromophore, and π^4s + π^2s cycloaddition of spiro[cyclohexa-2,4-diene-oxiran]-6-one are the key features of this approach. An efficient one-step synthesis of the epoxy ketone 11 by π^4s + π^2s cycloaddition of the in situ generated spiro[cyclohexa-2,4-diene-oxiran]one is reported. Further transformation of 11 to a variety of endo-tricyclo[5.2.2.0 ^2,6]undecanes (20, 25, 28, 30 and 31) and their photochemical behaviour upon singlet (¹S  ) excitation is described. Direct excitation of all the tricyclic chromophoric systems in benzene neatly furnished the protoilludanoids 32–36.

References

1. (a) A. Arnone, U. Brambilla, G. Nasini and O. Vajna dePava, Tetrahedron, 1995, 51, 13 357; (b) A. Arnone, G. Nasini, O. Vajna dePava and G. Assante, J. Chem. Soc., Perkin Trans. 1, 1992, 615; (c) D. M. X. Donnelly, R. M. Hutchinson, D. Coveney and M. Yonemitsu, Phytochemistry, 1990, 29, 2569; (d) D. M. X. Donnelly and R. M. Hutchinson, Phytochemistry, 1990, 29, 179; (e) A. Arnone, R. Cardillo, V. DiModugno and G. Nasini, J. Chem. Soc., Perkin Trans. 1, 1989, 1995; (f) T. C. McMorris, M. S. R. Nair and M. Anchel, J. Am. Chem. Soc., 1967, 89, 4562.
2. (a) E. P. Johnson and K. P. C. Vollhardt, J. Am. Chem. Soc., 1991, 113, 381 and references cited therein; (b) W. Oppolzer and A. Nakao, Tetrahedron Lett., 1986, 5471; (c) M. F. Semmelhack, S. Tomada, H. Nagaoka, S. Boettger and K. M. Hurst, J. Am. Chem. Soc., 1982, 104, 747; (d) J. Furukawa, N. Morisaki, H. Kobayashi, S. Iwasaki, S. Nozoe and S. Okuda, Chem. Pharm. Bull., 1985, 33, 440; (e) H. Takeshita, H. Iwabuchi, I. Kouno, M. Ino and D. Nomura, Chem. Lett., 1979, 649; (f) T. Matsumoto, K. Miyano, S. Kagawa, S. Yu, J. Ogawa and A. Ichibara, Tetrahedron Lett., 1971, 3521.
3. (a) W. A. Ayers and L. M. Browne, Tetrahedron, 1981, 37, 2199; (b) W. A. Ayers, T. T. Nakashima and M. H. Saeedighomi, Can. J. Chem., 1984, 62, 531; (c) H. Shirahama, E. Osawa and T. Matsumoto, J. Am. Chem. Soc., 1980, 102, 3208; (d) D. E. Cane and R. B. Nachbar, J. Am. Chem. Soc., 1978, 100, 3208; (e) N. Morisaki, J. Furukawa, H. Kobayashi, S. Iwasaki, S. Nozoe and S. Okuda, Tetrahedron Lett., 1985, 4755; (f) K. Hayano, Y. Ohfune, H. Shirahama and T. Matsumoto, Helv. Chim. Acta, 1981, 64, 1347.
4. (a) R. B. Woodward and R. Hoffman, Conservation of Orbital Symmetry, Academic Press, New York, 1972; (b) I. Fleming, Frontier Orbitals and Chemical Reactions, Wiley, Chichester, 1978.
5. V. K. Singh and M. Porinchu, J. Chem. Soc., Chem. Commun., 1993, 134.
6. A. J. Waring, Advances in Alicyclic Chemistry, eds. H. Hart, G. Karabatsos, Academic Press, New York, 1966, vol. 1, p. 131.
7. (a) E. Zibral, F. Wessely and H. Sturn, Mh. Chem., 1962, 93, 15; (b) W. Metlesicks, E. Schinzel, H. Vilcsek and F. Wessely, Mh. Chem., 1957, 88, 1069; (c) A. G. Schultz, J. P. Dittami, F. P. Lavieri, C. Salowey, P. Sundarraman and M. B. Szymula, J. Org. Chem., 1984, 49, 4429.
8. V. K. Singh and B. Thomas, J. Chem. Soc., Chem. Commun., 1992, 1211.
9. A. L. Wilds and D. J. Carl, J. Am. Chem. Soc., 1946, 68, 1862.
10. (a) L. M. Jackman and S. Sternhell, Application of NMR Spectroscopy in Organic Chemistry, Pergamon Press, New York, 1969; (b) A. P. Marchand, Stereochemical Application of NMR Studies in Bicyclic Systems, Verlag Chemie, International, Fl., 1982.
11. (a) G. C. Levy and G. L. Nelson, Carbon-13 Nuclear Magnetic Resonance for Organic Chemists, New York, 1977, vols. 1 and 2; (b) J. B. Stothers, C-13 NMR Spectroscopy, Academic Press, New York, 1973; (c) A. E. Derome, Modern NMR Techniques for Chemistry Research, Pergamon Press, Oxford, 1989.
12. (a) H. Labhat and G. Wagniere, Helv. Chim. Acta, 1959, 42, 2219; (b) D. E. Bays, R. C. Cookson and S. MacKenzie, J. Chem. Soc. B, 1967, 215; (c) V. K. Singh, P. T. Deota and A. V. Bedekar, J. Chem. Soc., Perkin Trans. 1, 1992, 903.
13. V. K. Singh and P. T. Deota, J. Chem. Res., 1989, (S), 390.
14. H. O. House, Modern Synthetic Reactions, W. A. Benzamin, Menlo Park, California, 1972.
15. (a) K. Bowden, H. Heilborn, E. R. H. Jones and B. C. L. Weedon, J. Chem. Soc., 1946, 39; (b) I. T. Harrison and S. Harrison, Compendium of Organic Synthetic Methods, Wiley Interscience, New York, 1971.
16. D. H. R. Barton and S. W. J. McCombie, J. Chem. Soc., Perkin Trans. 1, 1975, 1574.
17. (a) E. Bunnenberg, C. Djerassi, K. Mislow and A. Moseowitz, J. Am. Chem. Soc., 1962, 84, 2823; (b) A. Moscowitz, K. Mislow, M. A. W. Glass and C. Djerassi, J. Am. Chem. Soc., 1962, 84, 1945; (c) J. N. Murrel, The Theory of Electronic Spectra of Organic Molecules, Wiley, New York, 1963, p. 158.
18. G. Buchi and E. M. Burgess, J. Am. Chem. Soc., 1960, 82, 4333.
19. (a) K. N. Houk, Chem. Rev., 1976, 76, 1; (b) S. S. Hixon, P. S. Mariano and H. E. Zimmermann, Chem. Rev., 1973, 73, 531.
20. H. E. Zimmermann and D. Armesto, Chem. Rev., 1996, 96, 3065.
21. D. I. Schuster, Rearrangements in Ground and Excited States, ed. P. de Mayo, Academic Press, New York, vol. 3, 1980.
22. P. S. Engel and M. A. Schexnayder, J. Am. Chem. Soc., 1972, 94, 4357.
23. R. J. Chambers and B. A. Marples, Tetrahedron Lett., 1971, 3747.
24. R. L. Cargill, T. K. King, A. B. Sears and M. R. Willcot, J. Org. Chem., 1971, 36, 1423.
25. T. J. Eckerseley, S. D. Parker and N. A. J. Rogers, Tetrahedron, 1984, 40, 3749.
26. E. J. Corey and X. Chang, The Logic of Chemical Synthesis, John Wiley and Sons, Inc., New York, 1989.