Total Stereospecific Synthesis of (±)-Aklavinone

Journal of the American Chemical Society

Volumn 103, Issue 14, 1981, Pages 4251-4254

  Confalone, Pat N ^a   Pizzolato, Giacomo ^a  

^a HOFFMANN LA ROCHE INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AKLAVINONE;

DRUG ANALYSIS; DRUG IDENTIFICATION; DRUG STRUCTURE; DRUG SYNTHESIS; IN VITRO STUDY; NUCLEAR MAGNETIC RESONANCE; PRELIMINARY COMMUNICATION; THEORETICAL STUDY;

EID: 0019779298     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00404a048     Document Type: Article

References (16)

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10. Such borate esters have been postulated as intermediates in the Bohn-Schmidt reaction, which affords an overall hydroxylation of an anthraquinone. See: Bohn, R. German Patent 46654, 1889. Schmidt, R. E. Tetrahedron Lett. 60 855, 1891. Philips, M. Chem. Rev. 1929, 6, 168.
11. Oxidation of the acetate corresponding to 13 afforded a product ratio of 1.2, while the isobutyrate analogue yielded a ratio of 1.95. Difficulties in the formation of the isobutyrate analogue of 13 precluded its use, rendering the propionate 13 the substrate of choice.
12. The formation of transient intermediates along the path to 17 could be detected by TLC and are believed to be adducts of Me3SiCN and the aromatic carbonyls. The structure of 17 was assigned on thermodynamic grounds. See: Evans, D. A.; Hoffman, J. M.; Truesdale, L. K. J. Am. Chem. Soc. 1973, 95, 5822.
13. Roberts, R. M.; DeWolfe, R. H. J. Am. Chem. Soc. 1954, 76, 2411-2414. DeWolfe, R. H.; Augustine, F. B. J. Org. Chem. 1965, 30, 699-702.
14. Deslongchamps, P.; Tetrahedron 1975, 31, 2463-2490. Basic hydrolysis of the imidate ester 21 afforded the corresponding epoxy nitrile by a base catalyzed loss of methanol across the system.
15. Eckardt, K.; Bradler, G. Naturwissenschaften 1965, 52, 539. Eckardt, K. Chem. Ber. 1967,100, 2561. Our racemic synthetic sample had identical solution spectra and TLC behavior when compared to an authentic sample of galirubinone D (7-deoxyaklavinone) obtained by hydrogenolysis of natural aklavinone.
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