International audienceThe straightforward and ecofriendly preparation of functionalized julolidines starting from tetrahydroquinoline, diols, and aldehydes, for which water is produced as the only side product was investigated. To achieve this task, several well-defined ruthenium and iridium complexes including three new complexes were prepared from the corresponding phosphine–sulfonates, phosphine–carboxylates, and phosphine–phosphonates. The first transformation involved in situ generation of enaminoiminium intermediates, which allowed the formation of the julolidines through formal N,C(sp2)-cyclization of tetrahydroquinoline and the propane-1,3-diols. The influence of the chelate acidity points out that [Cp*IrIII]-based catalysts (Cp*=C5Me5) featuring phosphine–carboxylate and phosphine–sulfonate ligands were suitable for the cyclization, whereas the acidic phosphinophosphonate-containing complex favored the formation of reduced N-alkylated tetrahydroquinoline. We found that substitution of the propane-1,3-diols was crucial for the generation of enaminoiminium ions, which accounts for the efficiency and selectivity of the reaction. Applying another hydrogen autotransfer process, the prepared julolidines were easily functionalized at the C2 position

Context: The phytochemical study and biological activities of Astragalus armatus Willd. subsp. numidicus (Fabaceae) pods, an endemic shrub of Maghreb, are reported. Objective: This study isolates the secondary metabolites and determines the bioactivities of Astragalus armatus pods. Materials and methods: The chloroform, ethyl acetate and n-butanol extracts of hydro-ethanolic extracts were studied. Antioxidant activity was investigated using DPPH and ABTS radical scavenging, CUPRAC and ferrous chelating assays at concentrations ranging from 3 to 200 lg/mL. Anticholinesterase activity was determined against acetylcholinesterase and butyrylcholinesterase enzymes at 50, 100 and 200 lg/mL. Antibacterial activity was performed according to minimum inhibitory concentration (MIC) method. Carbon clearance method in albino mice was used for the phagocytic activity at concentrations 50, 70 and 100 mg/kg body weight. Spectroscopic techniques were used to elucidate the compounds. Results: Ethyl acetate extract afforded a flavonoid (1) while the n-butanol extract gave four flavonoids (2-5), a cyclitol (6) and a cycloartane-type saponin (7). The ethyl acetate extract exhibited highest antioxidant activity in DPPH (IC 50 : 67.90 ± 0.57 lg/mL), ABTS (IC 50 : 11.30 ± 0.09 lg/mL) and CUPRAC (A 0.50 : 50.60 ± 0.9 lg/mL) assays. The chloroform extract exhibited the best antibacterial activity against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa, each with 80 lg/mL MIC values. The nbutanol extract enhanced phagocytic activity. Discussion and conclusion:, pinitol (6) and cyclomacroside D (7) were isolated whereas 1, 2, 6 and 7 are reported for the first time from A. armatus.

A new phorbol-type diterpene ester, 4,20-dideoxy-4α-phorbol-12β-acetate-13α-isobutyrate, in addition to 11 known compounds were isolated from the latex and roots of Euphorbia clementei Boiss. Structure elucidation was performed by comprehensive 1D and 2D NMR analyses (H and C NMR, COSY, ROESY, HSQC and HMBC experiments), mass spectrometry (HR-ESI-MS) and by comparison with literature data. The inhibitory activity of all isolated compounds was evaluated against promyelocytic leukemia HL60 and human erythromyeloblastoid leukemia K562 cell lines and seven of these compounds exhibited a weak cytotoxicity with IC values ranging from 40 to 97 μM.

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International audienceAccess to 3,4- and 3,5-disubstituted piperidine derivatives has been achieved through [Cp*Ru]-catalyzed intermolecular coupling of allylic alcohols and propargylic amides. Tandem transformation was also possible via chemoselective [Cp*Ru]-catalyzed hydrogenation of the resulting homodienes