V. A. Denisenko

Monanchocidin: A New Apoptosis-Inducing Polycyclic Guanidine Alkaloid from the Marine Sponge Monanchora pulchra

Monanchocidin (1), a guanidine alkaloid with an unprecedented skeleton system derived from a polyketide precursor, (ω-3)-hydroxy fatty acid, and containing a 2-aminoethyl- and 3-aminopropyl-substituted morpholine hemiketal ring, has been isolated from the sponge Monanhora pulchra. The structure of 1 was assigned on the basis of detailed analysis of 1D and 2D NMR spectra, mass spectrometry, and results of chemical transformations. Compound 1 shows pro-apoptotic and cytoxic activities.

Monanchocidins B-E: polycyclic guanidine alkaloids with potent antileukemic activities from the sponge Monanchora pulchra.

New unusual polycyclic guanidine alkaloids monanchocidins B-E (2-5) along with monanchocidin A (1), which we recently described, were isolated from the Far-Eastern marine sponge Monanchora pulchra. Their structures were established using spectroscopic data and chemical transformations. Compounds 1-5 show potent cytotoxic activities against HL-60 human leukemia cells with IC50 values of 540, 200, 110, 830, and 650 nM, respectively.

Cyclosmenospongine, a new sesquiterpenoid aminoquinone from an Australian marine sponge Spongia sp.

A new sesquiterpenoid aminoquinone, cyclosmenospongine (1), containing a dihydropyran ring, was isolated from an Australian marine sponge Spongia sp., along with the known metabolites, smenospongiarine, ilimaquinone and smenospongine. The structure of 1 was determined from spectroscopic data.

Secondary metabolites from a marine-derived fungus Aspergillus carneus Blochwitz

Prenylated indole alkaloids, carneamides A-C (1-3), quinazolinone derivatives, carnequinazolines A-C (5-7), aryl C-glycosides, carnemycin A, B (8, 9) and a drimane sesquiterpenoid (10), together with known compounds (11-21) were isolated from the marine-derived fungus Aspergillus carneus (Trichocomaceae) KMM 4638. The antimicrobial and cytotoxic activities of the several alkaloids were examined.

Sesquiterpenoid aminoquinones from the marine sponge Dysidea sp.

Four new sesquiterpenoid arenarone derivatives, 18-aminoarenarone (1), 19-aminoarenarone (2), 18-methylaminoarenarone (3), and 19-methylaminoarenarone (4), and the new dimeric popolohuanone F (5), a derivative of 19-aminoarenarone (2) and arenarol (6), have been isolated from the Australian marine sponge Dysidea sp. together with the known compounds arenarol (6) and popolohuanone A (7). The structures of the new compounds 1-5 were established from extensive NMR spectroscopic data. Popolohuanones A (7) and F (5) and arenarol (6) showed DPPH radical scavenging activity with IC(50) values of 35, 35, and 19 microM, respectively.

Synthesis of Glycosides of Lupane-Type Triterpene Acids

A preparative synthesis of glucosides of the lupane-type triterpene acids betulinic, dihydrobetulinic, betulonic, dihydrobetulonic, and 3,20-dioxo-30-norlupan-28-oic was proposed. Glycosylation of 3-hydroxyacids by α-acetobromoglucose (ABG) with Ag2O was performed in pyridine (Py)to formglycosides at C-28, repeated glycosylation of which by these same reagents but in CH2Cl2 generated a glycoside bond at C-3 to form bisglucosides. 28-Glucosides of ketoacids were formed in high yields in both Py and CH2Cl2.

Synthesis of ginsenoside Rg3, a minor constituent of Ginseng Radix

Glycosylation of 12beta-acetoxy-dammar-24-en-3beta,20(S)-diol (4), with hepta-O-acetyl-alpha-sophorosyl bromide (5) under catalysis by Ag2CO3 or Ag2O afforded a chromatographically unseparated mixture of the alpha- and beta-linked octaacetates 6 and 7 in an approximately 2.5:1 ratio. After deprotection and chromatographic purification, the free alpha- (8) and beta-glycosides (9) were obtained. Sophoroside 9 was identical in all respects with ginsenoside Rg3, the minor component of Ginseng Radix rubra. All compounds were fully characterized by 1H and 13C NMR spectroscopy.

Pibocin, the first ergoline marine alkaloid from the Far-Eastern ascidian Eudistoma sp.

Abstract Pibocin 1 (1), the first representative of marine ergoline alkaloids, was isolated from the Far-Eastern ascidian Eudistoma sp. Its structure and absolute stereochemistry have been established as (8β)-2-bromo-6,8-dimethylergoline on the basis of spectroscopic and X-Ray analysis data. Pibocin showed moderate cytotoxic activity against mouse Ehrlich carcinoma cells.

Meroterpenoids from the alga-derived fungi Penicillium thomii maire and Penicillium lividum westling

Ten new austalide meroterpenoids (1-10) were isolated from the alga-derived fungi Penicillium thomii KMM 4645 and Penicillium lividum KMM 4663. Their structures were elucidated by extensive spectroscopic analysis and by comparison with related known compounds. The absolute configurations of some of the metabolites were assigned by the modified Moshers method and CD data. Compounds 1, 2, 8, and 9 were able to inhibit AP-1-dependent transcriptional activity in JB6 Cl41 cell lines at noncytotoxic concentrations. Austalides 1-5, 8, and 9 exhibited significant inhibitory activity against endo-1,3-β-D-glucanase from a crystalline stalk of the marine mollusk Pseudocardium sachalinensis.

Minor polyphenols from Maackia amurensis wood

The rare α,4,2′,4′-tetrahydroxydihydrochalcone, flavanones liquiritigenin and naringenin, isoflavones calycosin and 5-methoxydaidzein, and reduced stilbene dihydroresveratrol were isolated for the first time from Maackia amurensis wood. The structures of the pure compounds were established using 2D NMR COSY, NOE, HMBC, and HSQC experiments.