Minor and trace sterols in marine invertebrates. Part 20. 3ξ-Hydroxymethyl-A-nor-patinosterol and 3ξ-hydroxymethyl-A-nor-dinosterol. Two new sterols with modified nucleus and side-chain from the sponge Teichaxinella morchella

Abstract

The sponge Teichaxinella morchella from the Gulf of Mexico has been shown to contain solely 3F-hydroxymethyl-A-nor-sterols, of which two are the new 3~-hydroxymethyl-A-nor-patinosterol and 3t-hydroxymethyl-A-nordinosterol, isolated as acetates (1) and (1 2), respectively. The 24R and 24s epimers of both 24-methyl-[(4) and(5)] and 24-ethyl-[ ( 8) and (9)] 3~-acetoxymethyl-A-nor-5a-cholest-22-ene were separated by reverse-phase HPLC while the corresponding saturated compounds were isolated as epimeric pairs. The 360-MHz n.m.r. spectra of the 3-acetoxymethyl-A-nor-sterols are discussed. The sole occurrence of A-nor-sterols and the absence of conventional sterols suggest that they are, all bio-transformation products of dietary precursors. Attention is called to the potential chemo-taxonomic significance of this observation. A-NOR-STEROLShave previously been found in five different sponges from four different locations, namely Axinella verrucosa2 collected in the Bay of Naples, Stylotella agminata and Hornaxinella trachy from outside Palau in the West Carolines, an Axinella S P . ~ [0/948 Received, 20th June, ISSO]

Origin of petroleum in the Neoproterozoic–Cambrian South Oman Salt Basin

“…C 26 -C 28 A-norsteranes were detected in Cretaceous black shales of Italy (van Graas et al, 1982) and structural studies revealed that they contained a steroid-based skeleton with a five carbon A-ring. Interestingly, and perhaps significantly in this case, A-ring contraction is a feature of sterols in some sponges (Minale and Sodano, 1974;Bohlin et al, 1980Bohlin et al, , 1981. Short chain A-norsteranes have, however, never been described.…”

Terpenoids and Sterols from Mushrooms

“…1.21) [50,52,54]. Although a sterol with the (22E)-23,24-dimethyl-∆ 22 sterol side-chain has been detected in marine organisms [78], this is the first case of the isolation of a sterol with this side-chain in terrestrial sources. The stereochemistry at the configuration of the C-22 (23) double bond and C-24 was assigned as E and R, respectively, by comparison with the 1 H-NMR data reported for (22E)-23-methylergosta-5,22-dien-3b-ol (126) [77].…”

“…In addition to the known bioactive triterpene cucurbitacin B (76), two new cucurbitane-type triterpenoids, namely, leucopaxillones A (77) and B (78), have been isolated from the mushroom Leucopaxillus gentianeus (Fig. 1.13) [48].…”

Marine Natural Products from the Yucatan Peninsula

“…Pech-Puch et al reported in 2019 the isolation and structural characterization of seven terpenoids from the sponge Spongia tubulifera (now S. (Spongia) tubulifera) that were collected at Rio Indio, Quintana Roo state. Two of them resulted in being new natural products, 3β-hydroxyspongia-13(16),14-dien-2-one (15) and 19-dehydroxy-spongian diterpene 17 (16), while the remaining five corresponded to previously reported terpenes, three spongia furanoditerpenes: 9-nor-3-hydroxyspongia-3,13(16)14-trien-2-one (17), 3β, 19 dihydroxyspongia-13(16),14-dien-2-one (epispongiadiol) (18), and spongian diterpene 17 (19); the furanoditerpene ambliol C (20) and the sesterterpene scalarin (21). The pharmacological analysis of the isolated compounds displayed a very mild cytotoxic activity for 15, 18, and 20, while they showed no antimicrobial (Acinetobacter baumannii, Pseudomonas aeruginosa, Klebsiella pneumoniae, and Staphylococcus aureus) or antiviral (HAdV5 and HAdV5-GFP) activities [16] (Figure 4).…”

“…Additionally, 37 exhibited a moderate cytotoxic activity towards the Hep-2, MCF-7, and SiHa cell lines (CC50 of 10.5, 12.1, and 18.9 μg mL −1 /0.024, (30), and (22E,24R)-3E-acetoxymethyl-24-methyl-A-nor-5α-colest-22-ene (31) were isolated. Furthermore, four known steroids were also detected, (24S)-3E-acetoxymethyl -24-methyl-A-nor-5α-cholestane (32), (24R)-3E-acetoxymethyl-24-methyl-A-nor-5α-cholestane (33), (24R)-3E-acetoxymethyl-24-ethyl-A-nor-5α-cholestane (34), and (24S)-3E-acetoxymethyl-24-ethyl-A-nor -5α-cholestane (35) [18]. The relative configuration at C-3 and C-20 of 24-35 was not specified ( Figure 5), and no biological data were reported for these compounds.…”