E. E. Shul’ts

BIOLOGICALLY ACTIVE COMPOUNDS FROM Limonium Gmelinii AND L. Popovii. I

Compositions of ethylacetate fractions of roots and aerial parts of Limonium Gmelinii and L. Popovii (Plumbaginaceae) were studied. 3,5,7,3′,4′,6′-Hexahydroxyflavone and myricetin 3-O-α-L-(2′-galloyl)arabopyranoside, the structures of which were established using chemical transformations and spectral data, were isolated for the first time.

SYNTHESIS AND STUDY OF MUTAGENIC PROPERTIES OF LUPANE TRITERPENOIDS CONTAINING 1,2,3-TRIAZOLE FRAGMENTS IN THE C-30 POSITION

New derivatives of betulin, betulinic acid methyl ester, and their acetate analogs containing 1,2,3-triazole fragments in the C-30 position were synthesized. It was shown using the Ames test that 30-azidolup-20(29)-enes and 3β,28-diacetoxy-30-(4-R-1,2,3-triazol-1-yl)lup-20(29)-enes did not exhibit mutagenic properties.

Synthetic transformations of higher terpenoids: XXIV. Synthesis of cyanoethyl derivatives of lupane triterpenoids and their transformation into 1,2,4-oxadiazoles

Cyanoethylation of lupane triterpenoids was performed. Amide oximes of 3β-O-(2-cyanoethyl)-betulinic acid methyl ester and 3β-O-acetyl-28-O-(2-cyanoethyl)betulin and the corresponding O-[2-(1,2,4-oxadiazol-3-yl)ethyl] lupane derivatives were obtained.

SYNTHETIC TRANSFORMATIONS OF HIGHER TERPENOIDS. XXXIV. PREPARATION OF CARBOXYL DERIVATIVES OF ISOPIMARIC ACID

New isopimaric acid derivatives containing amines and methyl esters of α-, β-, and ω-amino acids were prepared. Conditions were found for cyclic isomerisation of isopimaric acid propargylamide into 2-(dodecahydrophenanthren-1-yl)-5-methyloxazole or 2-(dodecahydrophenanthren-1-yl)-5-methylene-4,5-dihydrooxazole. The latter was selectively modified by adding the methyl ester of (2-methylamino)butanoic acid at the oxazole C-5 position.

Furanoditerpenoids of the Labdane Series: Occurrence in Plants, Total Synthesis, Several Transformations, and Biological Activity

Structures of plant furanolabdanoids and synthetic schemes for a series of furanolabdanoids (coronarins A and E, hedychenone, acuminolide and 17-O-acetylacuminolide) from the available diterpenoids sclareol and larixol were reviewed. Attention was focused on transformations of available furanolabdanoids. Data on the biological activity of native metabolites and their synthetic derivatives were presented.

Study of plant coumarins. 1. Transformations of peucedanin

The structure of 2-bromooreoselon, which was prepared by bromination of peucedanin or oreoselon with molecular bromine, was established. The compositions and structures of the reaction products of this bromide with amines, such as pyridine, triethylamine, and morpholine, as well as with sodium acetate and potassium hydroxide were studied. The reaction of peucedanin with m-chloroperoxybenzoic acid affords peuruthenicin isobutyrate.

Role of cAMP- and IKK-2-Dependent Signaling Pathways in Functional Stimulation of Mesenchymal Progenitor Cells with Alkaloid Songorine

The role of cAMP- and IKK-2-dependent pathways in stimulation of the growth capacity of mesenchymal progenitor cells with alkaloid songorine was studied in vitro. Inhibitors of adenylate cyclase and IKK-2 were shown to abolish the increase in proliferative activity of progenitor cells. Moreover, blockade of the inhibitory kinase complex was accompanied by a decrease in the intensity of progenitor cell differentiation.

Synthetic transformations of higher terpenoids. XXVI. 16-acetylaminomethyllabdanoids and their cytotoxicity

Coupling of methyl 16-aminomethyllambertianate with N-Boc-protected ω-amino acids resulted in 16-(N-Boc-aminononan)- and 16-(N-Boc-aminoundecan)amidomethyllabdanoids. Interaction of methyl aminomethyllambertianate with bicyclo[2.2.1]hept-5-en-2,3-dicarboxylic acid anhydride led to the amide of bicyclo[2.2.1]heptan-1,2-dicarboxylic acid with a labdanoid substituent. Reaction of methyl 16-aminomethyllambertianate with chloroacetyl chloride resulted in methyl 16-(chloroacetylaminomethyl)lambertianate; coupling of the latter with methyl esters of amino acids gave the corresponding amides of methyl lambertianate. The compounds obtained were more cytotoxic toward CEM-13, MT-4, and U-937 tumor cell lines as compared with lambertianic acid; the dose inhibiting tumor cell viability by 50% (CCID50) of the more active compounds was 3.9–9.9 μM.

Synthetic transformations of higher terpenoids: XXIII. Synthesis of diterpenoid-based dihydroisoindolones

Vilsmeier-Haak reaction of phlomisoic acid methyl ester gave a mixture of 15- and 16-formyllabdanoids. In addition, methyl 2-formyldodecahydrophenanthro[1,2-b]furan-6-carboxylate was isolated, and its structure was determined by X-ray analysis. Reductive amination of 16-formyllabdanoid with benzylamine or α-amino acid methyl esters led to the formation of labdanoid furfurylamines which reacted with maleic anhydride to produce N-substituted 4-oxo-10-oxa-3-azatricyclo[5.2.1.01,5]dec-8-ene-6-carboxylic acids. Acylation of labdanoid furfurylamines with (E)-but-2-enoyl chloride afforded the corresponding unsaturated amides which were converted into 10-oxa-3-azatricyclo[5.2.1.01,5]dec-8-en-4-ones via intramolecular Diels-Alder reaction. Treatment of the oxa adducts with boron trifluoride-diethyl ether complex gave dihydroisoindol-1-one derivatives containing a diterpene fragment.

Synthetic transformations of higher terpenoids. XXI.* Preparation of phlomisoic acid and its N-containing derivatives

A method for preparing 15,16-epoxylabda-8(9),13(16),14-trien-18-oic (phlomisoic) acid was proposed. Its structure was confirmed by an XSA. N-containing derivatives of phlomisoic acid that contained amines, hydrazides, and methyl esters of amino acids on the C-18 atom in addition to (2-oxo-2-aminoacetyl)-substituted derivatives of the C-16 methyl ester of phlomisoic acid were prepared.