Vinyl Radical Cyclization. 2. Dicyclization via Selective Formation of Unsaturated Vinyl Radicals by Intramolecular Addition to Triple Bonds. Applications to the Synthesis of Butenolides and Furans

Journal of the American Chemical Society

Volumn 105, Issue 11, 1983, Pages 3720-3722

  Stork, Gilbert ^a   Mook, Robert ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000516559     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00349a067     Document Type: Letter

References (9)

1. Stork, G.; Baine, N.H. J. Am. Chem. Soc. 1982, 104, 2321.
2. Kharasch, M. S.; Jerome, J. J.; Urry, W. H. J. Org. Chem. 1950, 15, 966. Gazith, M.; Szwarc, M. J. Am. Chem. Soc. 1957, 79, 3339. Abel, P. I. In “Comprehensive Chemical Kinetics” Bamford, C. H., Tripper, C. F. H., Eds.; Elsevier: Amsterdam, 1976; Vol. 18. Giese, B.; Lachhein, S. Angew. Chem. 1982, 94, 780.
3. For a recent example of an intramolecular addition of a carbon-centered radical to a triple bond, see: Hart, D. J.; Choi, J.-K.; Tsai, Y.-M. Tetrahedron Lett. 1982, 23, 4765.
4. Reaction products were examined by capillary GLC, NMR, and IR spectroscopy and, in the case of 12, by mass spectrometry (M+ 284.286). Cyclizations were run under an argon atmosphere. Purification was by flash chromatography (Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923).
5. Lansbury, P. T.; Briggs, P. C.; Demmin, T. R.; DuBois, G.E. J. Am. Chem. Soc. 1971, 93, 1311.
6. The beneficial effect of β-alkoxy groups in radical cyclization reactions into a double bond has been noted: Beckwith, A. L. J.; Blair, I.; Phil-lipou, G. J. Am. Chem. Soc. 1974, 96, 1613.
7. For other recent work involving monocyclization of radicals derived from a-bromoacetals and olefins or acetylenes see: Ueno, Y.; Chino, K.; Watanabe, M.; Moriya, O.; Okawara, M. J. Am. Chem. Soc. 1982, 104, 5564. Okabe, M.; Tada, M. J. Org. Chem. 1982, 47, 5382. Our work involving cycloaddition of radicals with a β-acetal function, into olefinic as well as acetylenic systems was first reported in Mar 1982, on the occasion of the Edgar Fahs Smith lecture in Philadelphia. It was presented also at the Fourth International Conference on Organic Synthesis, Tokyo, Aug 1982. Cf. Nozaki, H., Ed. “Current Trends in Organic Synthesis” Pergamon Press: New York, 1983: pp. 359 ff.
8. For other recent routes to β-substituted furans, see (a) Tanis, S. P. Tetrahedron Lett. 1982, 23, 3115. (b) McMurry, J. E.; Donovan, S. F. Tetrahedron Lett. 1977, 2869.
9. These monocyclizations were also conveniently performed by using a polystyrene-supported tributyltin hydride first prepared in this laboratory by Gary Tennyson, following essentially the route described for the related dihydride (Weinshenker, N. M.; Crosby, G. A.; Wong, J.Y. J. Org. Chem. 1975, 40, 1966).