Abstract
The tributylstannane-induced cyclization of various chloro, thio, and selenoderivatives of carbonic and carboxylic acids were studied. It was found that the intramolecular addition of acyl radicals, or synthetic equivalents thereof, to double bonds follows regioselectively the exo-mode in the formation of both five and six membered rings. Alkyl-γ-lactones and thionolactones, as well as sixmembered cyclic oxo-compounds were obtained in high yields. The current understanding of the scope and limitations of these reactions are discussed.
Keywords
- Reductive Cyclization
- Acyl Radical
- Synthetic Equivalent
- Ring Transition State
- Intramolecular Hydrogen Transfer
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
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References
Hart, D.J. Science, 1984, 223, 883.
Giese, B. “Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds”, Pergamon Press, Oxford, 1986.
Ramaiah, M. Tetrahedron, 1987, 43, 3541.
Neumann, W.P. Synthesis, 1987, 665.
See for example:(a) Buchi, G.; Wuest, H. J. Org. Chem. 1979, 44, 546.
Bachi, M.D.; Hoornaert, C. Tetrahedron Lett. 1981, 22, 2689; 2693.
Bachi, M.D.; Hoornaert, C. Tetrahedron Lett. 1982, 23, 2025.
Hart, D.J.: Tsai, Y.-M. J. Am. Chem. Soc. 1982, 104, 1430.
Stork, G.; Baine, N.H. J. Am. Chem. Soc. 1982, 104, 2321.
Ueno, Y.; Chino, M.; Okawara, M. Tetrahedron Lett. 1982, 28, 2575.
Dulou, R.; Chretien-Bessiere, Y.; Desalbres, H. C.R. Acad. Sc. Ser. C, 1964, 258, 603.
Montheard, J.-P. C.R. Acad. Sc. Ser. C, 1965, 260, 577.
Chatzopoulos, M.; Montheard, J.-P. C.R. Acad. Sc. Ser. C, 1975, 280, 29.
Kampmeier, J.A.; Harris, S.H.; Wedegaertner, D.K. J. Org. Chem. 1980, 45, 315.
Cekovic, Z. Tetrahedron Lett. 1972, 749
Walsh, E.J. Jr.; Messinger, J.M.II; Grudoski, D.A. Allchin, C.A. Tetrahedron Lett. 1980, 21, 4409.
Davies, A.G.; Sutcliffe, R. J. Chem. Soc., Chem. Comm. 1979, 473.
Bachi, M.D.; Bosch, E. Tetrahedron Lett. 1986, 21, 641.
Bachi, M.D.; Bosch, E. Tetrahedron Lett. 1988, 29, 0000.
The stability of a thiocarbamate to tributylstannane was previously observed: Barton, D.H.R.; McCombie, S.W. J. Chem. Soc., Perkin I 1975, 1574.
For a similar decarboxylation, see: Beak, P.; Moje, S.W. J. Org. Chem. 1974, 89, 1320.
For example, the rate constant for decarboxylation of t-butyloxycarbonyl radical is 7.9xl05sec-1 at 80°C, see: Griller, D.; Roberts, B.P. J. Chem. Soc., Perkin Trans I. 1972, 747.
While the present work was in progress, the tributylstannane-induced cyclization of a seleno ester (32%), and the photolytically-induced cyclization of an acyl xanthate (70%)21 were reported.
Crich, D.; Fort, S.M. Tetrahedron Lett. 1987, 28, 2895.
Delduc, P.; Tailhan, C.; Zard, S.Z. J. Chem. Soc., Chem. Comm. 1988, 308.
Leonard, W.R.; Livinghouse, T. Tetrahedron Lett. 1985, 26, 6431.
A different approach to the synthesis of heterocyclic compounds through the intermediacy of imidoyl radicals was recently described: Leardini, R.; Tundo, A.; Zanardi, G.; Pedulli, G.F. Synthesis, 1985, 107.
Leardini, R.; Nanni, D.; Pedulli, G.F.; Tundo, A.; Zanardi, G.; J. Chem. Soc., Perkin Trans I 1986, 1591.
Padwa, A.; Nimmesgern, H.; Wong, G.S.K. J. Org. Chem. 1985, 50, 5620.
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© 1989 Kluwer Academic Publishers
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Bachi, M., Bosch, E., Denenmark, D., Girsh, D. (1989). ACYL, IMIDOYL, and Other Hetero-Substituted Free Radicals as Intermediates in the Synthesis of Cyclic Organic Compounds. In: Minisci, F. (eds) Free Radicals in Synthesis and Biology. NATO ASI Series, vol 260. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0897-0_11
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DOI: https://doi.org/10.1007/978-94-009-0897-0_11
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