Abstract
In connection with developing methods that would be applicable to the total synthesis of natural products such as sinularene (6), prezizaene (7), and quadrone (8), the thermolytic rearrangements of a number of substituted 6-(l-alkenyl)bicyclo[3.1.0]hex-2-enes were investigated. Upon thermolysis, compounds 9, 12, 36, 38, 42, 44, and 58 underwent clean [3,3]-sigmatropic (Cope) rearrangement to provide excellent yields of the functionalized bicyclo[3.2.1]octa-2,6-dienes 10, 15, 37, 30, 43, 45, and 59, respectively. In contrast, substances 29, 46, and 55 proved to be very poor substrates for Cope rearrangement. Thus, heating of these materials gave low yields or none of the corresponding Cope rearrangement products 30, 47, and 56, respectively.
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REFERENCES
C. Cupas, W.E. Watts, and P. von R. Schleyer, Tetrahedron Lett. 2503 (1964).
J.M. Brown, Chem. Commun. 226 (1965).
S.J. Rhoads and N.R. Raulins, Org. React. 22, 1 (1975).
E.M. Mil’vitskaya, A.V. Tarakanova, and A.V. Plate, Russ. Chem. Rev. 45, 469 (1976).
J.J. Gajewski, Hydrocarbon Thermal Isomerizations. Academic Press, Inc., New York, NY, 1981, pp. 215–216, 258-260.
J.E. Baldwin and K.E. Gilbert, J. Am. Chem. Soc. 98, 8283 (1976).
C.M. Beechan, C. Djerassi, J.S. Finer, and J. Clardy, Tetrahedron Lett. 2395 (1977).
E. Piers, G.L. Jung, and E.H. Ruediger, Can. J. Chem. 65, 670 (1987).
E. Piers and G.L. Jung, Can. J. Chem. 65, 1668 (1987).
C.W. Spangler, Chem. Rev. 76, 187 (1976).
R.J. Ellis and H.M. Frey, J. Chem. Soc. 5578 (1964).
W. Pickenhagen, F. Naf, G. Ohloff, P. Muller, and J.-C. Perlberger, Helv. Chim. Acta. 56, 1868 (1973).
Y. Ito, T. Hirao, and T. Saegusa, J. Org. Chem. 43, 1011 (1978).
P.J. Carrol, E.L. Ghisalberti, and D.E. Ralph, Phytochemistry. 15, 777 (1976).
E. Piers and P.S. Marrs, Unpublished work.
D. Seyferth, R.L. Lambert, Jr., and M. Massol, J. Organomet. Chem. 88, 255 (1975).
E. Piers, M. Jean, and P.S. Marrs, Tetrahedron Lett. 28, 5075 (1987).
P.K. Freeman and L.L. Hutchinson, J. Org. Chem. 48, 4705 (1983).
R.L. Ranieri and G.J. Calton, Tetrahedron Lett. 499 (1978); G.J. Calton, R.L. Ranieri, and M.A. Espenshade, J. Antibiot. 31, 38 (1978); K. Kon, K. Ito, and S. Isoe, Tetrahedron Lett. 25, 3739 (1984).
E. Piers, G.L. Jung, and N. Moss, Tetrahedron Lett. 25, 3959 (1984).
E. Piers and N. Moss, Unpublished work.
S. Burke, C.W. Murtiashaw, J.O. Saunders, J.A. Oplinger, and M.S. Dike, J. Am. Chem. Soc. 106, 4558 (1984).
E. Piers and N. Moss, Tetrahedron Lett. 26, 2735 (1985).
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© 1989 Kluwer Academic Publishers
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Piers, E. (1989). The Preparation and Thermal Rearrangement of Functionalized 6-(1-Alkenyl)Bicyclo[3.1.0]Hex-2-Enes. Applications to synthesis. In: de Meijere, A., Blechert, S. (eds) Strain and Its Implications in Organic Chemistry. NATO ASI Series, vol 273. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0929-8_3
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DOI: https://doi.org/10.1007/978-94-009-0929-8_3
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