Stereoselective formation of formal exo Diels-Alder adducts of silyloxydienes and allenecarboxylates [1]

Journal of the American Chemical Society

Volumn 121, Issue 14, 1999, Pages 3529-3530

  Jung, Michael E ^a   Nishimura, Nobuko ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; ALLENE DERIVATIVE; DYSIDIOLIDE; ENZYME INHIBITOR; UNCLASSIFIED DRUG;

CHEMICAL REACTION; CHEMICAL STRUCTURE; HEATING; HYDROGENATION; ISOLATION AND PURIFICATION; LETTER; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033553143     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9841660     Document Type: Letter

References (16)

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7. This diene was prepared by silylation of the kinetic enolate of E-3-penten-2-one.
8. (a) Jung, M. E.; Node, M.; Pfluger, R.; Lyster, M. A.; Lowe, J. A., III. J. Org. Chem. 1982, 47, 1150.
9. (b) Jung, M. E.; Lowe, J. A., III; Lyster, M. A.; Node, M.; Pfluger, R.; Brown, R. W. Tetrahedron 1984, 40, 4751.
10. (c) Spitzner, D.; Klein, I. Liebigs Ann. Chem. 1990, 63.
11. (d) Angew. Chem. 1982, 94, 639. In reference c, Spitzner and Klein report that their [2 + 2] cycloadduct does not rearrange to the [4 + 2] cycloadduct on heating.
12. (a) Dolbier, W. R., Jr.; Mancini, G. J. Tetrahedron Lett. 1975, 1141.
13. (b) Dolbier, W. R., Jr.; Piedrahita, C. A.; Al-Sader, B. H. Tetrahedron Lett. 1979, 2957.
14. We believe that the anion syn to the ester should be more stable than that syn to the methyl group, and thus, this determines which of the otherwise symmetrical C-C bonds of the cyclobutane ring is broken preferentially. Weiler showed several years ago that deprotonation of 3-methylbut-2-enoic acid salts with butyllithum in THF/HMPA gave nearly exclusively the anion syn to the acid. Harris, F. L.; Weiler, L. Tetrahedron Lett. 1985, 26, 1939.
15. Jung, M. E.; Houk, K. N., unpublished results.
16. The structures of all of the products were assigned by careful analysis of the high field proton NMR spectra, using coupling constants, 2D and nOe techniques heavily. Hydrolysis of the minor Diels-Alder adduct, 10n, afforded a crystalline enone, the structure of which was confirmed by single-crystal X-ray analysis. We thank Dr. Kenneth Hardcastle of the California State University, Northridge for that data.