Spiromarienonols A and B: Two New 7(8→9)abeo‐Lanostane‐Type Triterpene Lactones from the Stem Bark of Abies mariesii

Two new skeletal triterpene lactones, spiromarienonols A ( 1a ) and B ( 2a ), were isolated from the stem bark of Abies mariesii Masters (Pinaceae). Based on spectral data and biogenetic considerations, their unique three‐dimensional structures were determined to be (3R,7S,9R,23R)‐ ( 1a ) and (3R,7S,9S,23R)‐3,7‐dihydroxy‐8‐oxo‐7(8→9)abeo‐lanost‐24‐eno‐26,23‐lactone ( 2a ). Moreover, the potent activity of abiesenonic acid methyl ester ( 3 ) and abieslactone ( 4 ) against a disease‐oriented panel of 39 human cancer cell lines were investigated.     

Highly selective synthesis of 1‐phenylpentane‐1, 4‐diones,and (E)‐5‐hydroxy‐5‐phenylpent‐3‐en‐2‐ones catalyzed by organophosphorus compounds

1‐Phenylpentane‐1, 4‐diones, and (E)‐5‐hydroxy‐5‐phenylpent‐3‐en‐2‐ones were synthesized via organophosphine‐catalyzed addition reaction of but‐3‐en‐2‐one with aldehydes. The features of the present protocols include high selectivity, operational simplicity, atom economy, and mild reaction conditions without transition metals. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:425–430, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20568     

Sulfenylation of heterocyclic 1,3‐dicarbonyl systems: 4‐Hydroxy‐2‐pyrones, 6‐hydroxy‐4‐pyrimidones, 4‐hydroxy‐2‐pyridones, 4‐hydroxy‐6‐pyridazinones,and 5‐hydroxy‐3‐pyrazolones

Anions of enolized heteroaromatic 1,3‐dicarbonyl systems, such as the title compounds 1, 9,14 , and 19 , react in dimethylformamide in the presence of potassium carbonate with diaryl disulfides 2 to yield arylsulfenyl derivatives ( 3, 10, 15, 20 ). The arylthiolate anions 4 formed in this reaction can be oxidized by air to yield the starting disulfides 2 again. Tetraalkylthiuram disulfides 7 react in the same manner to yield dialkylaminothiocarbonylthio derivatives ( 8, 13, 18 ) of the title compounds. Oxidation of the arylsulfenyl derivatives with hydrogen peroxide in sodium hydroxide solution usually leads to sulfoxides ( 5, 11, 16 ), whereas oxidation with peracetic acid affords sulfones ( 6, 12, 17 ).     

New 20(10→5)abeo-Diterpenoids from Pygmaeopremna herbacea

Two new 20(10→5)abeo-abietune diterpenoids, pygmaeooins B ( 1 ) and C ( 2 ), have been isolated from the roots of Pygmaeopremna herbacea (Verbenaceae). Their structures were elucidated on the basis of spectroscopic data, and chemically, both compounds were correlated with each other. The absolute configurations were assigned tentatively on the basis of biogenetic pathway.     

Bis(5‐hydroxy‐2‐hydroxy­methyl‐4‐pyrone‐κ2O4,O5)bis(2‐hydroxy­methyl‐5‐oxido‐4‐pyrone‐κ2O4,O5)­calcium(II) tetrahydrate

In the title compound, [Ca(C₆H₅O₄)₂(C₆H₆O₄)₂]·4H₂O, which is a kojic acid–Ca²⁺ complex, the Ca atom is on a twofold axis and is octacoordinated by O atoms from four pyrone ligand mol­ecules. The hydroxyl and ketone O atoms of each ligand form a five‐membered chelate ring with the Ca atom. The crystal structure is stabilized by partial stacking and O—H?O hydrogen bonds.     

Micranthin C,a Novel 13(12→11)abeo‐Abietanoid from Isodon lophanthoids var. micranthus

A novel 13(12→11)abeo‐abietane skeletal diterpenoid, micranthin C ( 1 ), was isolated from Isodon lophanthoids var. micranthus. Its structure was determined by various spectroscopic techniques and finally confirmed by single‐crystal X‐ray diffraction.     

Hexaquacobalt(II) bis(5‐hydroxy‐7‐methoxy‐4‐oxo‐2‐phenyl‐4H‐chromene‐6‐sulfonate) tetrahydrate

The title compound, [Co(H₂O)₆](C₁₆H₁₁O₇S)₂·4H₂O, with cobalt(II) at the centre of symmetry, exhibits alternating hydrophilic and hydrophobic regions. Hydrophilic regions are generated by O—H...O hydrogen bonds among sulfonate groups, involving solvent water molecules and coordinated water molecules; π–π stacking interactions assemble the flavone skeletons into columns which form the hydrophobic regions. A three‐dimensional network is built up from an extensive array of hydrogen bonds, π–π stacking interactions and electrostatic interactions between the cation and anion. As a salt of the sulfonated derivative of naturally occurring tectochrysin (5‐hydroxy‐7‐methoxyflavone), this compound offers enhanced solubility and potential biological activity over the natural product.     

Supramolecular structure of racemic 5‐hydroxy‐4‐(4‐methoxyphenyl)‐10‐oxa‐4‐azatricyclo[5.2.1.02,6]dec‐8‐en‐3‐one

The structure of the title compound, C₁₅H₁₅NO₄, comprises a racemic mixture of chiral molecules containing five stereogenic centres. The cyclohexane ring tends towards a boat conformation and the two tetrahydrofuran rings adopt envelope conformations. Molecules are linked into sheets parallel to (100) by a combination of O—H...O, C—H...O and C—H...π hydrogen bonds, leading to a two‐dimensional supramolecular structure.     

Supramolecular networks of 10‐(2‐hydroxyethyl)acridin‐9(10H)‐one and 10‐(2‐chloroethyl)acridin‐9(10H)‐one

Both 10‐(2‐hydroxyethyl)acridin‐9(10H)‐one, C₁₅H₁₃NO₂, and 10‐(2‐chloroethyl)acridin‐9(10H)‐one, C₁₅H₁₂ClNO, have monoclinic (P2₁/c) symmetry and supramolecular three‐dimensional networks. But the differences in the intermolecular interactions displayed by the hydroxy group and the chlorine substituent lead to stronger intermolecular π‐stacking interactions and hydrogen bonding, and hence a significantly higher melting point for the former.     

Proton‐transfer compounds of 8‐hydroxy‐7‐iodoquinoline‐5‐sulfonic acid (ferron) with 4‐chloroaniline and 4‐bromoaniline

The crystal structures of the proton‐transfer compounds of ferron (8‐hydroxy‐7‐iodoquinoline‐5‐sulfonic acid) with 4‐chloroaniline and 4‐bromoaniline, namely 4‐chloroanilinium 8‐hydroxy‐7‐iodoquinoline‐5‐sulfonate monohydrate, C₆H₇ClN⁺·C₉H₅INO₄S⁻·H₂O, and 4‐bromoanilinium 8‐hydroxy‐7‐iodoquinoline‐5‐sulfonate monohydrate, C₆H₇BrN⁺·C₉H₅INO₄S⁻·H₂O, have been determined. The compounds are isomorphous and comprise sheets of hydrogen‐bonded cations, anions and water molecules which are extended into a three‐dimensional framework structure through centrosymmetric R₂²(10) O—H...N hydrogen‐bonded ferron dimer interactions.     

A New 18(13 → 12β)‐abeo‐Lanostadiene Triterpenoid from Ganoderma fornicatum

A new triterpenoid, fornicatin C (= (3β)‐3‐hydroxy‐18(13 → 12β)‐abeo‐lanosta‐13(17),24‐dien‐18‐oic acid; 1 ), was isolated from the fruiting bodies of Ganoderma fornicatum, together with the known compounds fornicatin A ( 2 ) and fornicatin B ( 3 ), among other constituents. The structure of 1 was elucidated by means of spectroscopic techniques, and those of 2 and 3 were identified by comparing their spectroscopic data with those reported in the literature.     

Two Novel 15(10→1)Abeomuurolane Sesquiterpenes from Cosmos sulphureus

Two novel 15(10→1)abeomuurolane sesquiterpenes, cosmosoic acid ( 1 ) and cosmosaldehyde ( 2 ), were isolated from the whole plant of Cosmos sulfurous. Their structures were established by a combination of 1D‐ and 2D‐NMR spectroscopic techniques. Additionally, a chemical correlation between 1 and 2 was also established.     

d‐Secoestrone derivatives. VI. 17β‐Benzyl‐17α‐hydroxy‐3‐methoxyestra‐1,3,5(10)‐trien‐16‐one

The title mol­ecule, C₂₆H₃₀O₃, shows a novel chemical rearrangement of the substituents at position 17, i.e. an α‐­orientation of the hydroxy group and a β‐orientation of the bulky benzyl moiety. The packing arrangement consists of coils formed by O2?O3 hydrogen bonds along the c axis. The compound shows complete loss of oestrogenic activity, and neither does it exhibit an antagonistic effect.