Electrochemical deacetoxylation: Synthesis of 11-ketotigogenin

Journal of Organic Chemistry

Volumn 61, Issue 1, 1996, Pages 405-407

  Mazur, D J ^a   Kendall, P M ^a   Murtiashaw, C W ^b   Dunn, P ^b   Pezzullo, S L ^b   Walinsky, S W ^b   Zung, J B ^b  

^a Electrosynthesis Co Inc   (United States)

^b PFIZER INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

11 OXOTIGOGENIN; CARDENOLIDE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; ELECTROCHEMISTRY; REACTION ANALYSIS;

EID: 0030028849     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9513469     Document Type: Article

References (14)

1. Djerassi, C.; Ringold, H. J.; Rosenkranz, G. J. Am. Chem. Soc. 1954, 76, 5533.
2. Chapman, J. H.; Elks, J.; Phillipps, G. H.; Wyman, L. J. J. Chem. Soc. 1956, 4344.
3. Djerassi, C.; Ringold, H. J.; Rosenkranz, G. J. Am. Chem. Soc. 1951, 73, 5513.
4. Kabasakalian, P.; McGlotten, J. Anal. Chem. 1959, 31, 1091.
5. Kabasakalian, P.; McGlotten, J.; Basch, A.; Yudis, M. D. J. Org. Chem. 1961, 26, 1738.
6. Rothman, E. S; Wall, M. E. J. Am. Chem. Soc. 1957, 79, 3228.
7. Tilak, B. V.; Sarangapani, S.; Weinberg, N. L. In Technique of Electroorganic Synthesis: Weinberg, N. L., Tilak, B. V., Eds.; John Wiley & Sons: New York, 1982; Vol. III, Chapter IV.
8. The lack of solubility of the starting material in solvents such as DMF or acetonitrile was a limiting factor, but the material is quite soluble in THF, and the use of this cosolvent gave the best overall results.
9. The relative amounts of 1a and 1b varied greatly from one experiment to another; inasmuch as the hydrolysis of 1b to 1a is presumably caused by cathodically generated base, it could be strongly dependent on the amount of adventitious moisture present in the system.
10. Torii, S.; Tanaka, H. In Organic Electrochemistry, 3rd ed.; Lund, H., Baizer, M. M., Eds.: Marcel Dekker: New York, 1991; Chapter 14.
11. Chaussard, J.; Folest, J. C.; Nedelec, J. Y.; Perichon, J.; Sibille, S.; Troupel, M. Synthesis 1990, 369 and references cited therein.
12. High surface area graphite felt (ESC Grade GF-S6) and ElectroCell electrochemical cells are available from the Electrosynthesis Co., Inc.
13. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.
14. The yield has not been optimized; in particular, we believe that the amount of 3a could very likely be reduced by more rigorous drying of the solvents and reagents.