Epoxide von Cardenoliden und Cardenolidglykosiden Partialsynthetische Versuche in der Reihe der Herzgifte. 1. Mitteilung

Sawlewicz, Ludwika; Linde, Horst H. A.; Meyer, Kuno

doi:10.1002/hlca.19680510618

Helvetica Chimica Acta

1968

DOI: 10.1002/hlca.19680510618

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Epoxide von Cardenoliden und Cardenolidglykosiden Partialsynthetische Versuche in der Reihe der Herzgifte. 1. Mitteilung

Ludwika Sawlewicz

Horst H. A. Linde

Kuno Meyer

Abstract: Die Partialsynthese der isomeren 4,5‐Epoxide des Canarigenins, des 3‐O‐[β‐D‐Digitoxopyranosido]‐4,5α‐epoxy‐canarigenins sowie der isomeren 14,15‐Epoxide des 14‐Anhydrodigitoxins und des 14,15β‐Epoxids des 14‐Anhydrodigoxins werden beschrieben.

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“…the hydroxyl groups of the sugar portion were protected as acetates. Regeneration of the alcohols was effected by mild hydrolysis with potassium bicarbonate at 37' for 15 days (17).…”

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confidence: 99%

Synthetic Cardenolides and Related Products. III. Isocardenolides

Ferland¹

1974

Can. J. Chem.

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The synthesis of novel cardenolides, closely related to naturally-occurring cardiotonic agents, is described. They were obtained from 17p- [3-furyl]androstanes derived from digitoxigenin, gitoxigenin, digoxigenin, and strophanthidin by hypohalous acid or organic peracid oxidation. The preparation of !3-D-and a-L-glycosidic derivatives is also reported.On a synthttise de nouveaux agents cardiotoniques, isomeres des cardenolides naturels. 11s ont tte obtenus par I'oxidation a l'aide de l'acide hypohaleux ou des peracides organiques de [3-furylI-17!3 androstanes, derives de la digitoxigenine, la digoxigenine, la gitoxigenine et la strophanthidine. Des dtrives B-D-et a-L-glycosidiques sont aussi decrits.Can. J. Chem.,52. 1652(1974) As part of a program aimed to improve the therapeutic ratio of cardiotonic agents, we prepared novel i~ocardenolides,~ which possessed all the characteristics of the natural cardenolides except for the location of the 0x0 group of the 5-membered lactone (3). In addition, 21-hydroxydigitoxigenin was also synthesized.When 17P-[3-furyl]-5p-androstane-3P, 14P-diol 3-acetate (26) was treated with a hypohalo~~s acid in aqueous dioxane, lactones 3a and 4 were isolated. The ma-ior product was 3a when 1 equiv. of the oxidant was used, while a larger excess of the reagent (2 equiv.) afforded mainly lactone 4. The structures were ascertained by spectral analyses (see Experimental). Furthermore, the aldehyde 4 was converted to the acid 5 and to the corresponding saturated lactone-aldehyde 6 by reducing the ene-dione system with zinc and acetic acid. Finally, 30 and 4 were both oxidized with potassium permanganate to the well-known ( 5 ) a-ketolactone 7. This constit~~tes an unanibig~~ous proof of the 17P-stereocheniistry of lactone 3u (Scheme 1).Scheme 2 illustrates a likely mechanism for the formation of 3a and 4. Initially an electrophilic attack of X + of the hypohalous acid on the lesshindered side of the furan ring, concerted with a n~~cleophilic addition of OH-, affords 9. Eliniination of HX, followed by rearrangement of the re-'For Parts I and I1 see refs. l a and b. 'This work was presented in part at the 6th International Symposi~~m on the Chemistry of N a t~~r a l Products, Mexico, April 22, 1969 (20).30ther types of isocardenolides and modified butenolides have been reported in the literature (4). suiting hydroxyfuran 10, yields 3a. In a competitive pathway further oxidation of 9 gives the bromolactone4 11, which is converted into 4 by an internal attack of the 14-hydroxyl on the carboxyl group with concomitant elimination of HX.The fury1 derivatives (2) were in general obtained by diisobutylaluminum hydride reduction of the natural cardenolides (1) (6). A n alternative process for the preparation of 2a was also used. Reduction of digitoxigenin l a with an excess diisobutylalumin~~m hydride afforded the diol 8, which was oxidized to 2a with 1 equiv. triethylamine -sulfur trioxide complex (7) (Scheme I). In this last process the key step involves the formation of an unstable lactol 13, w...

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“…the hydroxyl groups of the sugar portion were protected as acetates. Regeneration of the alcohols was effected by mild hydrolysis with potassium bicarbonate at 37' for 15 days (17).…”

mentioning

confidence: 99%

Synthetic Cardenolides and Related Products. III. Isocardenolides

Ferland¹

1974

Can. J. Chem.

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Gomphogenin‐Teilsynthese und Struktur des Calotropagenins. Glykoside und Aglykone, 319. Mitteilung

Lardon

Stöckel

Reichstein

1969

Helvetica Chimica Acta

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Gomphogenin = 2α, 3β, 14β‐trihydroxy‐5α‐card‐20:22‐enolide (6) was synthetised through hydroxylation of uzarigenone (4), followed by reduction with LiAlH[OC(CH3)3]3. Treatment of its di‐O‐acetylderivative (7) with SOCl2 in pyridine gave di‐O‐acetyl‐β‐anhydro‐gomphogenin (3). 3 was identical with the product obtained by WATSON AND WRIGHT from Gomphocarpus fruticosus; this proves that the formulae suggested by COOMBE AND WATSON are correct. From the mixture of about 7 unidentified cardenolides obtained by MITTAL et al. after WOLFF‐KISHNER reduction of ene‐dihydrocalactin we could now isolate and identify dihydrogomphogenin (6), dihydrocoroglaucigenin (11) and dihydro‐uzarigenin‐19‐acidlactone‐(19→3) (13). These results, together with former evidence and spectra, prove the structure of calotropagenin as 2α, 3β, 14β‐trihydroxy‐19‐oxo‐5α‐card‐20:22‐enolide (15) and give support to the formulation of calactin and calotropin as stereoisomers of formula 8, analogous to the formula of gomphoside established by COOMBE AND WATSON.

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3β‐Hydroxy‐14, 15β‐epoxy‐16β‐acetoxy‐5β, 14β‐card‐20(22)‐enolid aus Gitoxigenin. Partialsynthetische Versuche in der Reihe der Herzgifte, 4. Mitteilung [1]

Linde

Meyer

1970

Helvetica Chimica Acta

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Epoxide von Cardenoliden und Cardenolidglykosiden Partialsynthetische Versuche in der Reihe der Herzgifte. 1. Mitteilung

Abstract: Die Partialsynthese der isomeren 4,5‐Epoxide des Canarigenins, des 3‐O‐[β‐D‐Digitoxopyranosido]‐4,5α‐epoxy‐canarigenins sowie der isomeren 14,15‐Epoxide des 14‐Anhydrodigitoxins und des 14,15β‐Epoxids des 14‐Anhydrodigoxins werden beschrieben.

Cited by 15 publications

References 22 publications

Synthetic Cardenolides and Related Products. III. Isocardenolides

Synthetic Cardenolides and Related Products. III. Isocardenolides

Gomphogenin‐Teilsynthese und Struktur des Calotropagenins. Glykoside und Aglykone, 319. Mitteilung

3β‐Hydroxy‐14, 15β‐epoxy‐16β‐acetoxy‐5β, 14β‐card‐20(22)‐enolid aus Gitoxigenin. Partialsynthetische Versuche in der Reihe der Herzgifte, 4. Mitteilung [1]

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