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Bufadienolides. 8. 12(13→14)abeo skeletal rearrangements

Pettit, GR and Kasturi, TR and Knight, JC and Occolowitz, J (1970) Bufadienolides. 8. 12(13→14)abeo skeletal rearrangements. In: Journal of Organic Chemistry, 35 (5). pp. 1404-1410.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jo00830a032


Several methods were developed for converting isodigitoxigenin (2a) into methyl acetals 4b and 4c. Of these, methanolysis (followed by acetylation) of isodigitoxigenin in the presence of p-toluenesulfonic acid proved most useful. Each isomer reached an equilibrium corresponding to ca. 3:1 acetal 4c to 4b within 15 min in benzene containing p-toluenesulfonic acid. Addition of dihydropyran to the equilibrium mixture resulted in excellent conversion into vinyl ether 5a. Heating either acetal 4b or 4c in benzene containing p-toluenesulfonic acid led to a skeletal rearrangement culminating in formation of C-norcardenolide 6. In addition to results of physical measurements, the structure of spiran 6 was confirmed by degradation to methyl ketone 8. Similar rearrangement of isodigitoxigenin gave spiran 9 accompanied by C-norcardenolide 6. Treating lactone 9 with p-toluenesulfonic acid in methanol-water provided acetals 10a and 10b, which on further contact with p-toluenesulfonic acid in refluxing benzene gave lactone 9 and cardenolide 6. Evidence underlying the stereochemical assignments noted for structures 4, 9, and 10 was also discussed.

Item Type: Journal Article
Publication: Journal of Organic Chemistry
Publisher: American Chemical Society
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 20 May 2010 11:40
Last Modified: 05 Nov 2018 11:57
URI: http://eprints.iisc.ac.in/id/eprint/27958

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