Triterpene glycosides from Astragalus and their genins. LXXVIII. Chemical transformation of cycloartanes. VI. Partial synthesis of cycloadsurgenina

Cycloadsurgenin, 20R,24 S-epoxycycloartan-6α,25-diol-3,16-dione, was partially synthesized in four steps from cyclosieversigenin. Side products with the structures 17E,24S-cycloart-17-en-6α,24,25-triol-3,16-dione and 17Z,24 S-cycloart-17-en-6α,24,25-triol-3,16-dione were obtained in addition to the desired product. Presented at the 1st International Symposim on Edible Plant Resources and the Bioactive Ingredients, Xinjiang, China, July 25–27, 2008. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 591–595, November–December, 2008.     

Algal transformation of hydrocortisone by the cyanobacterium Nostoc ellipsosporum

The potential of Nostoc ellipsosporum for biotransformation of hydrocortisone was studied. The microorganism was isolated during a screening program from soil samples collected from the paddy fields in the north of Iran and had not been previously examined for this purpose. The biotransformation yielded 11β,17α,20β, 21-tetrahydroxypregn-4-en-3-one and 11β-hydroxyandrost-4-ene-3,17-dione. Both of the metabolites were purified chromatographically and characterized using instrumental analyses. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 572–574, November–December, 2006.     

Synthesis of 20S-protopanaxadiol 20-O-β-D-glucopyranoside, a metabolite of Panax ginseng glycosides, and compounds related to it

A preparative semi-synthetic method was developed to prepare 20S-protopanaxadiol 20-O-β-Dglucopyranoside (1), a metabolite of Panax ginseng glycosides. The 20-O-•-D-glucopyranosides of 20S-hydroxydammar-24-en-3,12-dione, 3β,20S-dihydroxydammar-24-en-12-one, and 3β,12α, 20S-trihydroxydammar-24-ene were synthesized for the first time. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 364–369, July–August, 2006.     

Glutinane triterpenes from the stem bark of <Emphasis Type="Italic">Euonymus hamiltonianus</Emphasis>

Three new glutinane-type triterpenes, 19α-glutin-5-en-19-ol (1), 2β,15α,21β-glutin-11-ene-2,15,21-triol (2), and 2β,19α-glutin-7,21-diene-2,19-diol (3), were isolated from the stem bark of Euonymus hamiltonianus. Their structures were determined by 1D and 2D NMR along with MS and IR. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 321–323, May–June, 2009.     

MS–MS Fragmentation Patterns of Cholesterol Oxidation Products

Summary. This study was aimed at analyzing the daughter ion spectra of 7 toxicologically relevant cholesterol oxidation products (COPs) i.e. cholestanetriol (cholestane-3β,5α,6β-triol), 7-ketocholesterol (cholest-5-en-3β-ol-7-one), 7α-hydroxycholesterol (cholest-5-en-3β,7α-diol), 7β-hydroxycholesterol (cholest-5-en-3β,7β-diol), 25-hydroxycholesterol (cholest-5-en-3β,25-diol), α-epoxycholesterol (cholestane-5α,6α-epoxy-3β-ol) and β-epoxycholesterol (cholestane-5β,6β-epoxy-3β-ol). In addition, 19-hydroxycholesterol (cholest-5-en-3β,19-diol) was analyzed as this serves as internal standard in COPs determination by HPLC-MS. Mass spectrometry was performed using a triple quadrupol mass spectrometer that was equipped with an APCI ion source. Our results indicate a common fragmentation pattern for COPs. The main breaking sites identified were in the sterol ring system between the carbon atoms with the position numbers 11–12, 12–13, and 8–14. Typical daughter ions of m/z = 81, 95, and 195 were used for multiple reaction monitoring analysis.     

Structures of new polar steroids from the Far-Eastern starfish <Emphasis Type="Italic">Ctenodiscus crispatus</Emphasis>

A fraction of sulfated polyhydroxylated steroids from the Far-Eastern starfish Ctenodiscus crispatus was investigated. The main component of this fraction was identified as (22E,24R,25R)-24-methyl-5α -cholest-22-en-3β,5,6β,15α,25,26-hexol 26-O-sulfate. For the compound stereoisomeric with respect to the side chain, the (24R,25S) or (24S,25R) relative configurations were assigned to the C(24) and C(25) chiral centers. The structures of two other compounds isolated from the fraction were identified as (22E, 24ξ)-26,27-bisnor-24-methyl-5α-cholest-22-en-3β,5,6β,15α,25-pentol 25-O-sulfate and (22E, 24ξ,25ξ)-24-methyl-5α-cholest-22-en-3β,5,6β,8,15α,25,26-heptol 26-O-sulfate. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1229–1234, May, 2005.     

Synthesis of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (chikusetsusaponin-LT8), a glycoside from Panax japonicus

A method for preparative production of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1), a glycoside from Panax japonicus, chikusetsusaponin-LT₈ was developed. Chemical transformation of betulafolientriol, a component of Betula leaves extract, produced the 12-keto-20S-protopanaxadiol (3β,20S-dihydroxydammar-24-en-12-one) (2), exhaustive glycosylation of which by 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosylbromide (3) under Koenigs—Knorr reaction conditions with subsequent removal of protecting groups formed 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1). The principal glycosylation product was 3β,20S-dihydroxydammar-24-en-12-one 3-O-β-D-glucopyranoside if equimolar amounts of (2) and (3) were used. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–48, January–February, 2006.     

A new component from <Emphasis Type="Italic">Eupatorium cannabinum</Emphasis>

A new compound of formula C₂₈H₄₈O with mp 179-180°C (aqueous ethanol) that was called eucanbin was isolated pure by column chromatography of the ethanol extract of the aerial part of Eupatorium cannabinum L. The structure 24α-methylcholest-20(21)-en-3β-ol was assigned based on chemical and spectral data. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 318–320, May–June, 2009.     

A new phytoecdysteroid

A new phytoecdysteroid,viz, 2-deoxy-3-epi-4β, 20-dihydroxycedysone ((20R,22R)-3α,4β 14α,20,22,25-hexahydroxy-5β-cholest-7-en-6-one), named coronatasteronc, was isolated fromSerratula coronata and identified by NMR spectroscopy. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1954–1955, November, 2000.     

Separation and identification of steroidal compounds with cytotoxic activity against human gastric cancer cell lines <Emphasis Type="Italic">in vitro</Emphasis> from the rhizomes of <Emphasis Type="Italic">Paris polyphylla</Emphasis> var. <Emphasis Type="Italic">chinensis</Emphasis>

A novel steroidal saponin, along with 12 known steroidal compounds, was isolated from the rhizomes of Paris polyphylla var. chinensis. Spectral data, including two-dimensional NMR, showed that the structure of the novel saponin was 3β,21-dihydroxypregnane-5-en-20S-(22,16)-lactone-1-O-α-L-rhamnopyranosyl(1→2)-[β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside. The isolated steroidal compounds were evaluated for their cytotoxic activity on human gastric cancer cell line HepG₂, SGC7901, BxPC3. Diosgenin-3-O-α-L-rhamnopyranosyl(1→2)[α-L-rabinofuranosyl(1→4)]-β-D-glucopyranoside exhibited the most potent cytotoxic activity among the isolated steroids. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 556–560, November–December, 2007.     

Separation and Determination of Eremophilenolides from Ligulariopsis shichuana by Capillary Zone Electrophoresis

A new method of capillary zone electrophoresis (CZE) was established by simultaneous assay of four eremophilenolides, 3β-acetoxy-9β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (1), 3β-senecioyloxy -1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (2), 6α-hydroxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (3) and 3β-acetoxy- 6β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (4) in the Chinese herbal extract from Ligulariopsis shichuana. The optimum buffer system was 20 mM borate buffer (pH 10.00). Voltage was 25 kV and detection at 214 nm. Regression equations revealed linear relationships (correlation coefficients 0.9986, 0.9990, 0.9992 and 0.9995) between the peak area of each compound and its concentration. The relative standard deviations of migration times and peak areas were <1.35 and 3.94% within 1 day, respectively. The effects of several CE parameters on the resolution were studied systematically. The contents of four eremophilenolides in Ligulariopsis shichuana were successfully determined with satisfactory repeatability and recovery.     

Triterpenoids from plants of the genus Tamarix

The taraxeran-14-ene-type triterpenoids methyl 3-β-al-D-fridoolean-14-en-28-oate (1), 3-α-[3″,4′-dihydroxytrans-cinnamoyl]-oxy-D-fridoolean-14-en-28-oic acid (2), and β-sitosterol (3) were isolated from the aerial part of plants from the genus Tamarix (T. laxa, T. elongata) (Tamaricaceae). The structures of the triterpenoids were proved using spectral data (IR, UV, PMR, ¹³C NMR, 2D NMR ¹H-¹H COSY, HMQC, HMBC, mass). Compound 1 is new and not previously described in the literature. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 271–273, May–June, 2006.     

Structure of a New Diterpene Alcohol from <Emphasis Type="Italic">Pinus sibirica</Emphasis> Buds

The newditerpene alcohol (1) in addition to the known metabolitesisoagatholal (2) and β-sitosterol glucoside (as the tetraacetate) (3) were isolated from buds of Siberian pine. The structure of the new compound was established as abieto-8(14)-en-18-ol 9α,13α-endoperoxide. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 343–344, July–August, 2005.     

Synthesis of D-seco-13α-Androst-5-ene Derivatives

Summary. 3β-Hydroxy-16,17-seco-13α-androsta-5,16-dien-17-al was obtained from 3β-acetoxyandrost-5-en-17-one in six steps with a Grob fragmentation as the key step. This seco-steroid, containing a formyl group and an unsaturated side-chain in a sterically favourable cis position, is a useful synthon for the synthesis of novel heterocycles condensed to the 3β-hydroxy-13α-androst-5-en-17-one skeleton.     

Structure of the repeat unit of the Alteromonas addita type strain KMM 3600T O-specific polysaccharide

The O-specific polysaccharide of Alteromonas addita type strain KMM 3600T is constructed of trisaccharide repeat units containing L-rhamnose, D-glucose, and D-galactose. It was established that the O-specific polysaccharide consists of trisaccharide repeat units with the structure →3)-α-D-Galp-(1→3)-α-L-Rhap-(1→3)-α-D-Glcp-(1→ based on monosaccharide analysis, Smith degradation, PMR and ¹³C NMR spectroscopy, and two-dimensional COSY, HSQC, and HMBC. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 445–447, September-October, 2008.     

Synthesis of 6α-methyl-16α,17α-cyclohexano-19-norprogesterone from a 19-methyl-6-desmethyl precursor

After prolonged refluxing of 19-tosyloxy-16α,17α-cyclohexanopregn-5-en-3β-ol-20-one (3) with NaI in 2-propanol, the initially formed 19-iodo derivative (4) undergoes supraface migration of the CH₂I group from the C(10) atom to the C(6) atom, probably through involvement of a homoallyl cation. The resulting 6β-iodomethyl-16α,17α-cyclohexano-19-norpregn-5(10)-en-3β-ol (5) was transformed in three steps into 6α-methyl-16α,17α-cyclohexano-19-norprogesterone (6α-methyl-19-nor-D′ ₆-pentarane,8). The transformation of compound5 into the target product8 also gave a side product, a pentarane with aromatic ringA (10), which was isolated and characterized by spectroscopic methods. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1688–1691, September, 1997.     

New thiazinediones and other components from Xanthium strumarium

Two new thiazinediones along with five known compounds were isolated from the fruits of Xanthium strumarium L. The structures of the two new compounds were determined to be 7-hydroxymethyl-8,8-dimethyl-4,8-dihydrobenzol[1,4]thiazine-3,5-dione-11-O-β-D-glucopyranoside (1) and 2-hydroxy-7-hydroxymethyl-8,8-dimethyl-4,8-dihydrobenzol[1,4]thiazine-3,5-dione-11-O-β-D-glucopyranoside (2). The five known compounds were identified as xanthiazone (3), chlorogenic acid (4), ferulic acid (5), formononetin (6), and ononin (7), respectively. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 456–458, September–October, 2006.     

Study on interaction between antibiotics and Escherichia coli DH5α by microcalorimetric method

A microcalorimetric technique based on the bacterial heat output was applied to evaluate the influence of antibiotics PIP (Piperacillin Sodium) and composite preparation of PIP and SBT (Sulbactam Sodium) on the growth of E. coli DH5α. The power–time curves of the growth metabolism of E. coli DH5α were studied using a TAM Air Isothermal Microcalorimeter at 37°C. By analyzing the power–time curves, the parameters such as growth rate constants (k), inhibitory ratio (I), the maximum heat power (P _m) and the time of the maximum heat power (t _m) were obtained. The results show that different concentrations of antibiotics affect the growth metabolism of E. coli DH5α. The PIP in the concentration range of 0–0.05 μg mL^–1 has a stimulatory effect on the E. coli DH5α growth, while the PIP of higher concentrations (0.05 –0.25 μg mL^–1) can inhibit its growth. It seems that the composite preparation composed of PIP and SBT cannot improve the inhibitory effect on E. coli DH5α as compared with the PIP.     

1-Acyldeoxyvasicinone salts as effective intermediate C-and N-acylating agents for alkaloids and amino acids

The reaction of deoxyvasicinone with acid chlorides of aliphatic (acetylbromide) and aromatic (benzoyl-, o-, p-methoxy-, p-nitrobenzoylchlorides) acids was studied. It was shown that 1-deoxyvasicinone salts were formed at room temperature; α-aroyloxymethylidenedeoxyvasicinones, in the presence of triethylamine at 80–85°C. It was found that acid chlorides cause 1-acyldeoxyvasicinone salts to transform into α-hydroxy-or α-aroyloxyarylidenedeoxyvasicinones, which indirectly confirmed their acylating properties. It was found that 1-acyldeoxyvasicinone salts were effective acylating agents for alkaloids (cytisine, 1,2-dihydrodeoxyvasicinone) and amino acids (glycine, β-alanine, α-aminobutyric acid) and can be used to acylate primary and secondary aliphatic and heterocyclic amines. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 585–589, November–December, 2006.     

Synthesis of 19β,28-epoxy-23,24-dinor-<Emphasis Type="Italic">A-neo</Emphasis>-18α-olean-4-en-3-one from betulin

19β,28-Epoxy-23,24-dinor-A-neo-18α-olean-4-en-3-one was obtained from betulin in a total yield of 18%. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 804–806, April, 2007.