Synthesis of Deuterium-Labeled Steroid 3,6-Diols

Abstract

A facile synthesis of a set of deuterium-labeled steroid 3,6-diols with different steroid A/B ring fusion, unsaturations, and configurations of hydroxyl groups at C-3 and C-6 is described. Reduction and deuteration, based on deuterium-exchange of the obtained the cholest-4-ene-3,6-dione from cholesterol using sodium borodeuteride and deuterium water, were used. The obtained steroid diols are intended to be used as precursors in the studies on biosynthesis of some marine polar steroids.

Two New Steroidal Monoglycosides, Anthenosides A1 and A2, and Revision of the Structure of Known Anthenoside A with Unusual Monosaccharide Residue from the Starfish Anthenea aspera

“…The value of the common coupling constant between H’-3 and H’-4 is 8.8 Hz and the value of the common coupling constant between H’-4 and H’-5 is 9.8 Hz. It is known that the values of the coupling constants of vicinal protons in the cyclohexane ring (chair conformation) occupying the axial-axial position are more than 5 Hz (usually 8–10 Hz) such as in glucopyranosyl, xylopyranosyl and quinovopyranosyl residues [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. The values of the coupling constants of vicinal protons in the cyclohexane ring (chair conformation) occupying the axial-equatorial position are less than 5 Hz (usually 2–4 Hz), as for example, in galactopyranosyl and fucopyranosyl residues [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ].…”

“…In addition, the values of coupling constants of H 3 -26/H-25 (6.7 Hz) and H 3 -27/H-25 (6.8 Hz) of 3 were refined. These are characteristic of methyl groups of aglycon side chain in starfish polar steroidal compounds [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. Previously, it was erroneously reported that the values of these coupling constants of anthenoside A were 11.5 Hz and 12.0 Hz, respectively [ 17 ].…”

“…As characteristic secondary metabolites of starfish (Echinodermata, Asteroidea) steroidal glycosides may be divided into three major classes: glycosides of polyhydroxysteroids, cyclic glycosides, and asterosaponins [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. Starfish steroidal glycosides have been reported to show a wide spectrum of biological activities [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ]. Polyhydroxysteroidal glycosides from starfish have highly oxygenated steroidal aglycons and in most cases monosaccharides of these compounds are represented by β- d -xylopyranosyl and α- l -arabinofuranosyl residues or their methylated or sulfated derivatives.…”

New Triterpene Glycosides from the Far Eastern Starfish Solaster pacificus and Their Biological Activity

“…At the same time, polar steroids and their glycosides are characteristic secondary metabolites of starfish (sea stars). The starfish steroidal glycosides may be divided into three major classes: glycosides of polyhydroxysteroids, cyclic glycosides, and asterosaponins [ 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ]. Polyhydroxysteroidal glycosides from starfish have highly oxygenated steroidal aglycon.…”

In Vitro Anticancer and Proapoptotic Activities of Steroidal Glycosides from the Starfish Anthenea aspera

“…Starfishes are known to contain diverse types of secondary metabolites possessing a wide spectrum of biological activities, including cytotoxic, antibacterial, neuritogenic, antifungal, cancer preventive, anti-inflammatory, and other effects [ 6 , 7 , 8 , 9 , 10 , 11 , 12 ]. At the same time, steroidal glycosides (glycosides of polyhydroxysteroids, cyclic glycosides, and asterosaponins) are common secondary metabolites of starfish.…”