Synthetic new cardenolides

Ferland, Jean-Marie; Lefebvre, Y.; Deghenghi, Romano; Wiesner, K.

doi:10.1016/s0040-4039(01)82838-0

Cited by 27 publications

(17 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The removal of a urethane requires either strong alkali or a hydride reduction, both incompatible with the cardenolide system. This was solved by using the fury1 precursor IV [6] as aglycone in the glycosylation. The finished deprotected digitoxoside was then converted into a cardenolide (V-+VI-tVII) or isocardenolide (V -tVIII) by rn -chloroperbenzoic acid and NaBH, or NBS, respectively [61.…”

mentioning

confidence: 99%

See 1 more Smart Citation

On Cardioactive Steroids. XVI. Stereoselective β‐Glycosylation of Digitoxose: The Synthesis of Digitoxin

Wiesner

Tsai

Jin

1985

Helvetica Chimica Acta

View full text Add to dashboard Cite

Two methods for stereoselective b-glycosylation of digitoxose were developed. The first achieved stereocontrol by a 1,3-participation of a N-methylurethane group under acid catalysis. The second utilized mercuric-ion catalyzed cleavage of thioglycosides and a 1,3-participation of ap-methoxybenzoyl group in a neutral medium. The first highly stereoselective and quite eficient synthesis of digitoxin (C7) was achieved by a combination of these methods. The furyl-substituted precursor IV of digitoxigenin (Scheme I) was used as aglycone, and the furan group was converted to the unsaturated lactone of digitoxin by our known oxidation procedure ( M -chloroperbenzoic acid/NaBH,) after the assembly of the carbohydrate portion of the molecule and its deblocking was completed.Introduction. -In previous communications of this series, we have described a novel and efficient methodology for the synthesis of cardenolides, bufadienolides and their analogues. As a result of this technique, we were able to synthesize up to now some 50

show abstract

mentioning

confidence: 99%

“…It was identical in all respects with an authentic sample of digitoxin. Alternatively, oxidation of C6 with NBS [6] followed by chromatography and crystallization gave 64.9 "LO of isodigitoxin C8.…”

mentioning

confidence: 99%

On Cardioactive Steroids. XVI. Stereoselective β‐Glycosylation of Digitoxose: The Synthesis of Digitoxin

Wiesner

Tsai

Jin

1985

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…The crude 3a was deprotected with n-Bu 4 NF in THF at reflux temperature to give 3b in quantitative yield from 2. From the 14β-methoxy derivative 3a the 14β-methoxydigitoxigenin 6b could be obtained by the oxidative/reductive procedure [6] shown in Scheme 2. The crude 3a was reacted with m-chloroperbenzoic acid in CHCl 3 in the presence of AcOH and AcONa; the crude hydroxy lactone intermediates 4 and 5 were reduced with NaBH 4 in CH 2 Cl 2 /water to give a mixture of the desired digitoxigenin derivative 6a and of the isomeric isodigitoxigenin derivative 7a in a 8:2 ratio.…”

Section: Resultsmentioning

confidence: 99%

“…Only a 3β-glucoside derivative of digitoxigenin-14β-methoxy has been described [10], for which the inotropic activity was reported to be marginal, but no synthetic route was given. Isodigitoxigenin [6] 17β-(4-Pyridazynil) [7] Digitoxigenin 17β-(3-Furyl) 14β,15β-epoxy [8] 14β,15β-epoxy [9] Figure 1. Parent compounds.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Biological Evaluation of 14 -Methoxy Digitalis Derivatives

Gobbini¹,

Almirante²,

Cerri³

et al. 1998

Molecules

View full text Add to dashboard Cite

Abstract:The synthesis and biological evaluation of 14β-methoxy derivatives of digitoxigenin and of other digitalis-like compounds are reported. These compounds have a 14β-oxygen, which can be a hydrogen bonding acceptor, as is the case of 14β,15β-epoxide derivatives, but not a hydrogen bonding donor as is the case of 14β-hydroxy derivatives. All the new 14β-methoxy derivatives show a considerable reduced binding affinity on Na + ,K + -ATPase when compared with the 14 β-hydroxy analogues and also with the 14β,15β-epoxy derivatives. These results could mean that the digitalis receptor does not permit the presence of a bulky substituent in the 14β region, even of relatively small volume like the methyl group.

show abstract

“…For the separation of the anomers 5, it is necessary to deblock R l or both R , and R,. The major p-anomer 6 was oxidized as described previously (7,8) and yielded the known P-digitoxoside 7 (2). We believe that the intermediate responsable for the steric control observed is not the urethane 8 but the charged species 9.…”

mentioning

confidence: 78%

On the synthesis of cardioactive steroid glycosides. On cardioactive steroids. XI

Jin¹,

Tsai²,

Wiesner³

1983

Can. J. Chem.

View full text Add to dashboard Cite

A stereoselective β-glycosidation of digitoxose and digitoxigenin involving a 1–3 participation of a urethane group is described. The conversion of digitoxin (10) to its furyl derivative 11 and the rcoxidation of 11 to digitoxin and isodigitoxin (12), respectively, in high yield is reported for the first time. This is of fundamental importance for the use of the new glycosidation method in the total synthesis of digitoxin and its analogues.

show abstract

Synthetic new cardenolides

Cited by 27 publications

References 2 publications

On Cardioactive Steroids. XVI. Stereoselective β‐Glycosylation of Digitoxose: The Synthesis of Digitoxin

On Cardioactive Steroids. XVI. Stereoselective β‐Glycosylation of Digitoxose: The Synthesis of Digitoxin

Synthesis and Biological Evaluation of 14 -Methoxy Digitalis Derivatives

On the synthesis of cardioactive steroid glycosides. On cardioactive steroids. XI

Contact Info

Product

Resources

About