Synthesis of (±)-Prostaglandin E1, (±)-11-Deoxyprostaglandins E1, F1α, and F1β, and (±)-9-Oxo-13-cis-prostenoic Acid by Conjugate Addition of Vinylcopper Reagents

Journal of the American Chemical Society

Volumn 94, Issue 22, 1972, Pages 7823-7827

  Alvarez, Francisco S ^a   Wren, Douglas ^a   Prince, Anthony ^a  

^a Syntex Research Institute of Organic Chemistry   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; PROSTAGLANDIN; VINYL DERIVATIVE;

ARTICLE; SYNTHESIS; TECHNIQUE;

COPPER; INDICATORS AND REAGENTS; METHODS; PROSTAGLANDINS; VINYL COMPOUNDS;

EID: 0015432571     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00777a026     Document Type: Article

References (16)

1. Studies in Prostaglandins. IX. For part VIII see P. Crabbe, Res. Prostaglandins, 1 (4), 5 (1972).
2. For recent reviews see: Ann. N. Y. Acad. Sci., 180 (1971);
3. J. E. Pike, Fortschr. Chem. Org. Naturst., 28, 313 (1971).
4. The preparation of 7,6-unsaturated ketones via conjugate addition of bisvinyl(tri-n-butylphosphine)copper lithium to cyclohexenones has been reported by J. Hooz and R. B. Layton, Can. J. Chem., 48, 1626 (1970).
5. Following the completion of this work, C. J. Sih, R. G. Salsman, P. Price, G. Peruzzotti, and R. Sood (J. Chem. Soc., Chem. Commun. 240 (1972))
6. 1 by addition of a functionalized organocopper reagent to 1a.
7. This compound, as the ethyl ester, has been reported by J. F. Bagli, T. Bogri, R. Deghenghi, and K. Wiesner, Tetrahedron Lett., 465 (1966). We have prepared this product by a different route, via the enol acetate of 2-(6″-methoxycarbonylhexyl)-1-cyclopentanone, followed by bromination with NBS in aqueous THF at room temperature and dehydrobromination with lithium carbonate in pyridine solution at 90–100° for 1 hr. We thank Professor G. Stork for unpublished information from his laboratory.
8. L. Heslinga, M. Van Gorkom, and D. A. Van Dorp, Recl. Trav. Chim. Pays. Bas, 87, 1421 (1968).
9. J. J. Pappas, W. P. Keaveney, E. Gaucher, and M. Berger, Tetrahedron Lett., 4273 (1966).
10. E. J. Corey, N. M. Weinschenker, T. K. Schaaf, and W. Huber, J. Amer. Chem. Soc., 91, 5675 (1969).
11. K. Bowden, I. M. Heilbron, E. R. H. Jones, and B. C. L. Weedon, J. Chem. Soc., 39 (1946).
12. Reported: 112–113°; H. L. Slates, Z. S. Zelamski, D. Taub, and N. L. Wendler J. Chem. Soc., Chem. Commun., 6, 305 (1972).
13. 1 as a mixture of stereoisomers has been reported; cf. J. F. Bagli, T. Bogri, R. Deghenghi, and K. Wiesner, Tetrahedron Lett., 465 (1966), and
14. M. P. L. Caton, E. C. J. Coffe, and G. L. Watkins, Tetrahedron Lett., 773 (1972).
15. 13C nmr studies. This analysis will be the subject of a separate report: M. Maddox, F. Alvarez, and L. Tökés, J. Chem. Soc. Chem. Commun., submitted for publication.
16. Reported mp 112–113°: H. L. Slates, Z. S. Zelamski, D. Taub, and N. L. Wendler, J. Chem. Soc. Chem. Commun., 6, 305 (1972).