Dedicated to the memory of Prof. Roberto F. Souza, one of the pioneers of ionic liquid phase organometallic catalysisThe reaction of [BMI·Cl] (BMI = 1-butyl-3-methylimidazolium) or [BMMI·Cl] (BMMI = 3-butyl-1,2-dimethylimidazolium) with Ru 3 (CO) 12 generates Ru-hydride-carbonyl-carbene species in situ that are efficient catalysts for a reverse water gas shift/ hydroformylation/hydrogenation cascade reaction. The addition of H 3 PO 4 increased the catalytic activity of the first step (i.e., the hydrogenation of CO 2 to CO). Under the optimized reaction conditions [120 8C and 6.0 MPa CO 2 /H 2 (1:1) for 17 h], cyclohexene and 2,2-disubstituted alkenes were easily functionalized to alcohols through sequential hydroformylation/carbonyl reduction.Carbon dioxide sequestration and its use as a feedstock in industrial processes are major challenges in the development of alternative greener and sustainable processes. [1] Indeed, several catalytic processes are under investigation, and they include the incorporation of CO 2 through the addition to epoxides to generate organic carbonates, diols, and polycarbonates by using either organic or metal-based catalysts. [2] However, the substitution of carbon monoxide (CO) by carbon dioxide (CO 2 ) in carbonylation reactions [3][4][5][6] may allow for new applications with broader use for this important and abundant but poorly reactive substrate. Indeed, at the industrial scale, the hydroformylation [7,8] of alkenes is one of the most important applications of homogeneous catalysis, and over 9 million tons of socalled oxo products, such as aldehydes and alcohols, are produced each year. [9] Rh-modified systems are the catalysts of choice for this reaction, as they are highly active and selective for the formation of aldehydes, [7,8] as well as for cascade reactions involving hydroformylation/Witting, [10] hydroaminomethylation sequences, [11,12] and hydroformylation/cyclization reactions. [13][14][15][16] Other metals, such as Pt and Ru, have been much less studied owing to their high hydrogenation activity, which results in the formation of large amounts of alkanes as byproducts. [17][18][19][20] However, the use of Rh-Ru bimetallic systems is of interest for the production of alcohols by hydroformylation/hydrogenation se-quences. [21][22][23][24][25] The differences in selectivity could be easily understood if we look at the hydroformylation and hydrogenation mechanisms catalyzed by Rh I and Ru 0 systems, as the active catalytic species under hydroformylation conditions are the RhÀH and the RuÀ(H) 2 species. [7][8][9]26] The accepted mechanism for the formation of MÀ(H) 2 is the homolytic cleavage of the HÀH bond, as the formation of MÀH occurs either by intramolecular (ligands) or intermolecular (external base) heterolysis of the HÀH bond, which favors the formation of MÀH species. [12,27,28] For instance, cationic [RuÀH] + species species are described as the catallytically active species in the Ru-catalyzed hydrogenation of acids, cyclic carbonates, and CO 2 to alcohol. [...

Lichens are unique individuals which have been widely used in traditional medicines. This study was focused on the bioassayguided phytochemical investigation, and bioactivity evaluation on a lichens species, Parmotrema cooperi. This first bioassaydirected chemical study on P. cooperi has led to the isolation of ethyl heamatomate (1), atraric acid (2), ethyl orsellinate (3), orsellinic acid (4), lecanoric acid (5), gyrophoric acid (6), and licanorin (7). The structures of 17 were mainly elucidated from spectroscopic methods including 1D, and 2D NMR spectroscopy, and mass spectrometry. These compounds were evaluated for their antiglycation, urease, α-chymotrypsin, and β-glucoronidase inhibitory activities. Few of the phenolic compounds showed significant, while most of them showed good inhibition of protein glycation, and urease activities.lichen, Parmotrema cooperi, ethyl heamatomate, atraric acid, urease inhibition, antiglycation

The catalytic species generated by dissolving Ru3 (CO)12 in the ionic liquids 1-n-butyl-3-methyl-imidazolium chloride or 1-n-butyl-2,3-dimethyl-imidazolium chloride are efficient multifunctional catalysts for: (a) reverse water-gas shift, (b) hydroformylation of alkenes, and (c) reductive amination of aldehydes. Thus the reaction of alkenes with primary or secondary amines (alkene/amine, 1:1) under CO2 /H2 (1:1) affords the hydroaminomethylations products in high alkene conversions (up to 99 %) and selectivities (up to 96 %). The reaction proceeds under relatively mild reaction conditions (120 °C, 60 bar=6 MPa) and affords selectively secondary and tertiary amines. The presence of amine strongly reduces the alkene hydrogenation competitive pathway usually observed in the hydroformylation of terminal alkenes by Ru complexes. The catalytic system is also highly active for the reductive amination of aldehydes and ketones yielding amines in high yields (>90 %).

Two new prenylated flavonoids, thunbergiols A (1) and B (2), along with three known compounds, chrysin (3), quercetin (4) and berberine (5) were obtained from the methanolic extract of roots of Berberis thunbergii DC. MS, NMR and other spectroscopic techniques were employed for their structural characterisation.