Chemical Degradation of Sarverogenin, Proof for the Presence of the Steroid Carbon Skeleton. Glycosides and Aglycones, 335th Communication

Abstract

Chemical degradation of sarverogenin (1) to several bile‐acid derivatives of known structures is described. This is a proof that 1 contains the normal tetracyclic steroid skeleton, and that the structure suggested for 1 by Fuhrer et al. [3] on the basis of spectral data is correct.

The Cytotoxic Cardiac Glycoside (−)-Cryptanoside A from the Stems ofCryptolepis dubiaand Its Molecular Targets

“…31 It was hence proposed as 7,8β-epoxy-3β,11α,17β-trihydroxy-12-oxo-5βcard-20 (22)-enolide by analysis of the IR, NMR, and mass spectra of this cardenolide, 32 as supported by degradation of sarverogenin to several known bile-acid derivatives. 33 Thus far, (−)-cryptanoside A (1) has been identified from different plant parts of C. dubia and assigned with several names. Its structure was proposed by analysis of its spectroscopic data and confirmed using its hydrolyzed products sarverogenin and L-oleandrose, but its NMR spectroscopic data were not assigned correctly, and its absolute configuration was not determined unambiguously by any of these previous investigations.…”

“…A 7,15α-oxide unit was assigned in the original structure of sarverogenin through a series of chemical reactions, but such an assignment was found to be ambiguous when investigating the NMR spectroscopic data of sarverogenin acetate . It was hence proposed as 7,8β-epoxy-3β,11α,17β-trihydroxy-12-oxo-5β-card-20(22)-enolide by analysis of the IR, NMR, and mass spectra of this cardenolide, as supported by degradation of sarverogenin to several known bile-acid derivatives …”

Chemie der Kohlenhydrate, der Pflanzeninhaltsstoffe und der mikrobiellen Stoffwechselprodukte im Spiegel der Helvetica Chimica Acta 1918–1992

“…Gleichzeitig gelang es, durch schonende Extraktionsmethoden, die enzymatische und andere Spaltungen verhindern, die genuinen Glycoside von Digitalis Ianuta, die Digilanide A, B und C 1691, und etwas spater die Purpureaglucoside A und B aus Digitalis purpurea [79] rein zu isolieren. Uber die Reinheit der Glycoside von Digitalis Zunata kam es zu einer Kontroverse mit C. Mannich, Berlin-Dahlem [71] (Fig.…”

Steroids: reactions and partial syntheses

“…The chemical degradation of the plant aglycone, sarverogenin, to several known bile acid derivatives establishes that it contains the steroid skeleton, and confirms the structure (271) proposed in 1969 on the basis of spectroscopic data. 170 Further applications of the [2,3]Wittig and [3,3]Claisen rearrangements in side-chain synthesis allow stereocontrolled 280) is obtained by reaction of the acid (279) with thionyl chloride in the presence of an excess of pyridine, followed by quenching with methanol. Cleavage of the sulphine group is readily achieved with a variety of oxidants, but for large-scale work the best method is non-oxidative and involves treatment of the sulphine (280) with acetic anhydride in the presence of catalytic amounts of sulphuric acid.…”