Chemical characterisation of essential oils of leaves of two Solanaceae: Solanum rugosum and Solanum erianthum from Côte d'Ivoire.

This study made it possible to characterise by GC (in combination with retention indices), GC-MS and 13C NMR, the chemical composition of the essential oils from Solanum rugosum and Solanum erianthum, two Solanaceae of the Ivorian flora. The two essential oils were characterised by a very high proportion of sesquiterpenes. Specifically, the essential oil of S. rugosum was dominated by (E)-ß-caryophyllene (33.7%), ß-elemol (19.8%) and germacrene D (14.4%), while that of S. erianthum was mainly composed of α-humulene (38.6%), ß-elemol (17.8%) and (E)-ß-caryophyllene (16.7%). The chemical composition of Solanum rugosum is described here for the first time.

Golden Face of Phosphine: Cascade Reaction to Bridgehead Methanophosphocines by Intramolecular Double Hydroarylation.

Reported herein is the first example of a gold-catalyzed cyclization of bis(arylmethyl)ethynylphosphine oxides. This represents an original approach to bridgehead methanophosphocines 1, eight-membered heterocycles. Gold catalyst in combination with triflic acid activates alkyne and induces a double hydroarylation. Mechanistic studies suggest that the reaction proceeds stepwise, forming first the 1 H-isophosphinoline 2-oxide 5. Reduction and protection of the corresponding phosphine oxides 1 described herein also highlight the effectiveness of our approach to this new class of electron-rich ligands.

Preliminary Structure-Activity Relationship (SAR) of a Novel Series of Pyrazole SKF-96365 Analogues as Potential Store-Operated Calcium Entry (SOCE) Inhibitors.

From a series of (1R, 1S)-1[ß-(phenylalkoxy)-(phenetyl)]-1H-pyrazolium hydrochloride as new analogues of SKF-96365, one has an interesting effect for endoplasmic reticulum (ER) Ca2+ release and store-operated Ca2+ entry (SOCE) (IC50 25 µM) on the PLP-B lymphocyte cell line. A successful resolution of (±) 1-phenyl-2-(1H-pyrazol-1-yl)ethan-1-ol has been developed by using the method of "half-concentration" in the presence of (+)-(1S)- or (-)-(1R)-CSA.

Chemical findings and in vitro biological studies to uphold the use of Ficus exasperata Vahl leaf and stem bark.

Ficus exasperata Vahl, commonly known as sandpaper, is a terrestrial Afro-tropical tree used in popular medicine. Despite the existence of some works on the biological activities of this species, its chemical composition is still poorly known. The aim of this study was to extend the knowledge on the phytochemistry and biological properties of this species. Aqueous extracts from F. exasperata leaves and stem bark were analysed. Thirty-one phenolic compounds, comprising cinnamoyl derivatives, flavonoid-O-glycosides, flavonoid-mono-C-glycosides, flavonoid-di-C-glycosides and one furanocoumarin, were determined by HPLC-DAD-ESI/MSn and UPLC-ESI-QTOF-MS, 26 of them being reported for the first time in this species. The profile of organic acids, characterized by HPLC-UV, was also reported for the first time. The best radical scavenging activity was observed for the aqueous extract from leaves (IC50 values of 222.5, 510.0 and 50.0 µg/mL against DPPH•, •NO and O2•-, respectively). In addition, both aqueous extracts of the leaves and stem bark displayed a weak effect on α-amylase, and no cytotoxicity against gastric adenocarcinoma cell line, AGS. This study contributes to the valorisation of these vegetal materials, which may have application in functional foods and/or nutraceuticals.

Chemical composition of the leaf oil of Artabotrys jollyanus from Côte d'Ivoire

ABSTRACT One oil sample isolated from leaves of Artabotrys jollyanus Pierre, Annonaceae, from Côte d'Ivoire has been analyzed by GC(RI), GC-MS and 13C NMR. In total, thirty-seven compounds accounting for 96.9% of the relative composition have been identified. The composition of the essential oil was dominated by trans-calamenene (15.7%), α-copaene (14.8%), α-cubebene (10.4%), cadina-3,5-diene (10.3%), (E)-β-caryophyllene (6.3%) and cadina-1,4-diene (6.1%). 13C NMR spectroscopy was very useful in the identification of trans-calamenene, 7-hydroxycalamenene, cadina-3,5-diene and cadina-1,4-diene. Moreover, monitoring the evolution of the leaf essential oil composition and the yield on a 12-month period (one sample per month) was achieved. The twelve essential oil samples exhibited a chemical homogeneity but the yield varied from sample to sample (0.26-0.60%).

Chemical composition of Ivorian Artabotrys insignis leaf oil. Combined analysis including 13C NMR, to quantify germacrene A and ß-elemene.

The chemical composition of leaf essential oil from Artabotrys insignis Engler & Diels collected from Cote d'Ivoire was determined by GC(FID), GC-MS and 13C NMR. The main compounds were ß-elemene (66.8%) and germacrene A (17.1%). The true content of germacrene A/ß-elemene was obtained by combining GC(FID) and 13C NMR data.

Composition and Chemical Variability of Cleistopholis patens Trunk Bark Oil from Côte d'Ivoire.

The chemical composition of trunk bark oil from Cleistopholis patens (Benth.) Engl. & Diels, growing wild in Côte d'Ivoire, has been investigated by GC (FID) in combination with retention indices, GC/MS and 13 C-NMR. Moreover, one oil sample has been subjected to CC and all the fractions analyzed by GC (RI) and 13 C-NMR. In total, 61 components have been identified, including various sesquiterpene esters scarcely found in essential oils. 13 C-NMR was particularly efficient for the identification of a component not eluted on GC and for the quantification of heat-sensitive compounds. Then, 36 oil samples, isolated from trunk bark harvested in six Ivoirian forests have been analyzed. The content of the main components varied drastically from sample to sample: (E)-ß-caryophyllene (0.4 - 69.1%), ß-pinene (0 - 57%), α-phellandrene (0 - 33.2%), α-pinene (0.1 - 30.6%), ß-elemol (0.1 - 29.9%), germacrene D (0 - 25.4%), juvenile hormone III (0 - 22.9%), germacrene B (0 - 20.6%) and sabinene (tr-20.3%). Statistical analysis, hierarchical clustering and principal components analysis, carried out on the 36 compositions evidenced a fair chemical variability of the stem bark oil of this species. Indeed, three clusters have been distinguished: the composition of group I (ten samples) was dominated by ß-pinene and α-pinene, group II (nine samples) was represented by α-phellandrene and p-cymene and group III (16 samples) by ß-elemol. A sample displayed an atypical composition dominated by (E)-ß-caryophyllene.

Composition and Chemical Variability of Ivoirian Polyalthia oliveri Leaf Oil.

The chemical composition of 45 essential oil samples isolated from the leaves of Polyalthia oliveri harvested in three Ivoirian forests was investigated by GC-FID (retention indices measured on two columns of different polarities), and by (13) C-NMR, following a method developed in our laboratory. In total, 41 components were identified. The content of the main components varied drastically from sample to sample: (E)-ß-caryophyllene (1.2 - 50.8%), α-humulene (0.6 - 47.7%), isoguaiene (0 - 27.9%), alloaromadendrene (0 - 24.7%), germacrene B (0 - 18.3%), δ-cadinene (0.4 - 19.3%), and ß-selinene (0.2 - 18.5%). The analysis of six oil samples selected in function of their chromatographic profiles is reported in detail. The 45 oil compositions were submitted to hierarchical cluster and principal components analysis, which allowed the distinction of three groups within the oil samples. The compositions of the oils from group I (15 samples) and II (12 samples) were dominated by (E)-ß-caryophyllene and α-humulene, respectively. Oil samples of group III (18 samples) needed to be partitioned into four subgroups III.1-III.4 whose compositions were dominated by alloaromadenrene, isoguaiene, germacrene B, and δ-cadinene, respectively.

Synthetic Development of New 3-(4-Arylmethylamino)butyl-5-arylidene-rhodanines under Microwave Irradiation and Their Effects on Tumor Cell Lines and against Protein Kinases.

A new route to 3-(4-arylmethylamino)butyl-5-arylidene-2-thioxo-1,3-thiazolidine-4-one 9 was developed in six steps from commercial 1,4-diaminobutane 1 as starting material. The key step of this multi-step synthesis involved a solution phase "one-pot two-steps" approach assisted by microwave dielectric from N-(arylmethyl)butane-1,4-diamine hydrochloride 6a-f (as source of the first point diversity) and commercial bis-(carboxymethyl)-trithiocarbonate reagent 7 for construction of the rhodanine platform. This platform was immediately functionalized by Knoevenagel condensation under microwave irradiation with a series of aromatic aldehydes 3 as second point of diversity. These new compounds were prepared in moderate to good yields and the fourteen synthetic products 9a-n have been obtained with a Z-geometry about their exocyclic double bond. These new 5-arylidene rhodanines derivatives 9a-n were tested for their kinase inhibitory potencies against four protein kinases: Human cyclin-dependent kinase 5-p25, HsCDK5-p25; porcine Glycogen Synthase Kinase-3, GSK-3α/ß; porcine Casein Kinase 1, SsCK1 and human HsHaspin. They have also been evaluated for their in vitro inhibition of cell proliferation (HuH7 D12, Caco 2, MDA-MB 231, HCT 116, PC3, NCI-H727, HaCat and fibroblasts). Among of all these compounds, 9j presented selective micromolar inhibition activity on SsCK1 and 9i exhibited antitumor activities in the HuH7 D12, MDA-MBD231 cell lines.

HPLC Analysis and Cytotoxicity of n-Butanol Extract from Glyphaea brevis Roots Against C6 Glioma Cells.

The n-butanol extract of the roots of Glyphaea brevis was analysed. HPLC analysis suggested the presence of phenolic compounds like protocatechuic acid (PCA). The extract showed moderate cytotoxic activity against C6 glioma cells (EC50 > 1 mg/ml).

Synthesis of New N,N'-Bis(5-arylidene-4-oxo-4,5-dihydrothiazolin-2-yl)piperazine Derivatives Under Microwave Irradiation and Preliminary Biological Evaluation.

New N,N'-bis(5-arylidene-4-oxo-4,5-dihydrothiazoline-2-yl)diamine derivatives 5 were prepared in two steps from rhodanine and piperazine, or 1,4-bis(3-amino-propyl)piperazine, under microwave reaction conditions with retention of configuration. Some of these compounds were tested for in vitro antiproliferative activities and for their kinase inhibitory potencies towards six kinases (CDK5/p25, GSK3α/ß, DYRK1A, DYRK2, CLK1, and CLK2). The compound 5d showed nanomolar activity towards DYRK1A kinase (IC(50) = 0.041 µM).

Synthesis of N,N'-bis(5-arylidene-4-oxo-3,5-dihydro-4H-imidazol-2-yl)diamines bearing various linkers and biological evaluation as potential inhibitors of kinases.

The synthesis in 4 steps of new N,N'-bis(5-arylidene-4-oxo-3,5-dihydro-4H-imidazol-2-yl)diamines issued from various symmetric primary diamines as linkers was reported. The key step of our strategy has been the sulphur/nitrogen displacement of (5Z)-5-arylidene-2-ethylsulfanyl-3,5-dihydro-4H-imidazol-4-ones 6 with respectively ethylenediamine 7a, piperazine 7b and N,N'-bis(3-aminopropyl)piperazine 7c using solvent-free reaction conditions under microwave irradiation with retention of configuration. These compounds were tested for their kinase inhibitory potencies toward four kinases (GSK-3α/ß, DYRK1A, CLK1 and CLK3).