5,10-<i>seco</i>-<i>neo</i>-Clerodanes and <i>neo</i>-Clerodanes from <i>Salvia microphylla</i>

Two new 5,10-<i>seco</i>-<i>neo</i>-clerodanes, salvimicrophyllins A and B (<b>1</b> and <b>2</b>), and two new <i>neo</i>-clerodanes, salvimicrophyllins C and D (<b>3</b> and <b>4</b>), were isolated from the leaves and flowers of <i>Salvia microphylla</i>. The structures of these compounds were elucidated mainly by analysis of their NMR spectroscopic and mass spectrometric data. The relative configurations of the salvimicrophyllins were determined by analysis of NOESY spectra and ECD curves, and the relative configuration of compound <b>2</b> was confirmed by single-crystal X-ray diffraction crystallography

An Enantioselective Approach to Furanoeremophilanes: (+)‑9‑Oxoeuryopsin

An enantioselective total synthesis of the furanoeremophilane sesquiterpene (+)-9-oxoeuryopsin <b>1</b> is reported. The synthesis involves as a key step a copper­(II) triflate catalyzed tandem asymmetric conjugate addition of AlMe₃ to 2-methyl-2-cyclohexen-1-one with the Feringa (<i>S</i>,<i>R,R</i>)-phosphoramidite binaphthol ligand, followed by aldol condensation of the resulting aluminum enolate with 4-methyl-3-furaldehyde <b>4</b>. This tandem transformation has not been previously reported with a 2-substituted-2-cyclohexen-1-one. Conventional functional group manipulations completed the synthesis

An Enantioselective Approach to Furanoeremophilanes: (+)‑9‑Oxoeuryopsin

An enantioselective total synthesis of the furanoeremophilane sesquiterpene (+)-9-oxoeuryopsin <b>1</b> is reported. The synthesis involves as a key step a copper­(II) triflate catalyzed tandem asymmetric conjugate addition of AlMe₃ to 2-methyl-2-cyclohexen-1-one with the Feringa (<i>S</i>,<i>R,R</i>)-phosphoramidite binaphthol ligand, followed by aldol condensation of the resulting aluminum enolate with 4-methyl-3-furaldehyde <b>4</b>. This tandem transformation has not been previously reported with a 2-substituted-2-cyclohexen-1-one. Conventional functional group manipulations completed the synthesis

An Enantioselective Approach to Furanoeremophilanes: (+)‑9‑Oxoeuryopsin

An enantioselective total synthesis of the furanoeremophilane sesquiterpene (+)-9-oxoeuryopsin <b>1</b> is reported. The synthesis involves as a key step a copper­(II) triflate catalyzed tandem asymmetric conjugate addition of AlMe₃ to 2-methyl-2-cyclohexen-1-one with the Feringa (<i>S</i>,<i>R,R</i>)-phosphoramidite binaphthol ligand, followed by aldol condensation of the resulting aluminum enolate with 4-methyl-3-furaldehyde <b>4</b>. This tandem transformation has not been previously reported with a 2-substituted-2-cyclohexen-1-one. Conventional functional group manipulations completed the synthesis

An Enantioselective Approach to Furanoeremophilanes: (+)‑9‑Oxoeuryopsin

An enantioselective total synthesis of the furanoeremophilane sesquiterpene (+)-9-oxoeuryopsin <b>1</b> is reported. The synthesis involves as a key step a copper­(II) triflate catalyzed tandem asymmetric conjugate addition of AlMe₃ to 2-methyl-2-cyclohexen-1-one with the Feringa (<i>S</i>,<i>R,R</i>)-phosphoramidite binaphthol ligand, followed by aldol condensation of the resulting aluminum enolate with 4-methyl-3-furaldehyde <b>4</b>. This tandem transformation has not been previously reported with a 2-substituted-2-cyclohexen-1-one. Conventional functional group manipulations completed the synthesis

Teotihuacanin, a Diterpene with an Unusual Spiro-10/6 System from <i>Salvia amarissima</i> with Potent Modulatory Activity of Multidrug Resistance in Cancer Cells

Teotihuacanin (<b>1</b>), an unusual rearranged clerodane diterpene with a new carbon skeleton containing a spiro-10/6 bicyclic system, was isolated from the leaves and flowers of <i>Salvia amarissima</i>. Its structure was determined through spectroscopic analyses. Its absolute configuration was established by single-crystal X-ray diffraction. Compound <b>1</b> showed potent modulatory activity of multidrug resistance in vinblastine-resistant MCF-7 cancer cell line (reversal fold, RF_MCF‑7/Vin+ > 10703) at 25 μg/mL

Stress testing as an instrument for bank liquidity risk assessment

У статті проводиться узагальнення теоретичних аспектів оцінки ризику ліквідності на основі застосування методики стрес-тестування. Уточнено класифікацію стрес-тестів та механізм проведення стрес-тестування на рівні окремих портфелів банку.The article is devoted to the generalization of the theoretical aspects of the liquidity risk estimation on the basis of application of stress testing method. The classification of stress tests and the mechanism of carrying out of stress testing at the level of separate portfolios of bank are specified

Ferrocenylselenoamides: Synthesis, Characterization and Cytotoxic Properties

A new series of ferrocenyl selenoamides <b>7</b>–<b>11</b> (FcSeNH­(CH₂)<i>_n</i>CH₂(R)­OH, <i>n</i> = 1, 2, 3, R = H, Me, Ph) were prepared in good yields by selenative demetalation of Fischer aminocarbene complexes. The crystal structures of <b>7</b> [FcSeNH­(CH₂)₂OH] and <b>19</b> [PhSeNH­(CH₂)₂OH] reveal their capability to form intermolecular hydrogen bonding in solid state. Results of SRB assays show that these new selenium compounds have a good anticancer potency superior to tamoxifen and cisplatin, with IC₅₀ values ranging from 4.5 to 13.32 μM against human breast cancer cell lines. A preliminary model to explain the structure–cytotoxic activity relation is proposed where different structural parameters such as the alkyl chain length, the presence of bulky groups in the same chain, the effect of hydroxyl group, and also the role of ferrocene moiety are included as being responsible for the cytotoxic response

<i>neo</i>-Clerodane Diterpenoids from <i>Salvia polystachya</i> Stimulate the Expression of Extracellular Matrix Components in Human Dermal Fibroblasts

Eleven <i>neo</i>-clerodane diterpenoids (<b>1</b>–<b>11</b>) including the new analogues <b>1</b>, <b>2</b>, and <b>10</b>, and 3′,5,6,7-tetrahydroxy-4′-methoxyflavone (<b>12</b>) were isolated from the aerial parts of <i>Salvia polystachya.</i> Polystachyne G (<b>1</b>) and 15-<i>epi</i>-polystachyne G (<b>2</b>) were isolated as an epimeric mixture, containing a 5-hydroxyfuran-2­(5<i>H</i>)-one unit in the side chain at C-12 of the <i>neo-</i>clerodane framework. Polystachyne H (<b>10</b>) contains a 1(10),2-diene moiety and a tertiary C-4 hydroxy group. The structures of these compounds were established by analysis of their NMR spectroscopic and MS spectrometric data. The absolute configurations of compounds <b>3</b>, <b>4</b>, and <b>10</b> were determined through single-crystal X-ray diffraction analysis. The antibacterial, antifungal, and phytotoxic activities of the diterpenoids were determined. In addition, the stimulatory effect of the expression of extracellular matrix components of nine of the isolates (<b>1</b>–<b>8</b> and <b>11</b>) was assayed. Compounds <b>1</b>–<b>4</b>, <b>8</b>, and <b>11</b> increased the expression of the genes codifying for type I, type III, and type V collagens and for elastin

Ferrocenylselenoamides: Synthesis, Characterization and Cytotoxic Properties

A new series of ferrocenyl selenoamides <b>7</b>–<b>11</b> (FcSeNH­(CH₂)<i>_n</i>CH₂(R)­OH, <i>n</i> = 1, 2, 3, R = H, Me, Ph) were prepared in good yields by selenative demetalation of Fischer aminocarbene complexes. The crystal structures of <b>7</b> [FcSeNH­(CH₂)₂OH] and <b>19</b> [PhSeNH­(CH₂)₂OH] reveal their capability to form intermolecular hydrogen bonding in solid state. Results of SRB assays show that these new selenium compounds have a good anticancer potency superior to tamoxifen and cisplatin, with IC₅₀ values ranging from 4.5 to 13.32 μM against human breast cancer cell lines. A preliminary model to explain the structure–cytotoxic activity relation is proposed where different structural parameters such as the alkyl chain length, the presence of bulky groups in the same chain, the effect of hydroxyl group, and also the role of ferrocene moiety are included as being responsible for the cytotoxic response