Chiral rhodium complexes covalently anchored on carbon nanotubes for enantioselective hydrogenation

Chiral rhodium hybrid nanocatalysts have been prepared by covalent anchorage of pyrrolidine-based diphosphine ligands onto functionalized CNTs. This work constitutes the first attempt at covalent anchoring of homogeneous chiral catalysts on CNTs. The catalysts, prepared with two different chiral phosphines, were characterized by ICP, XPS, N2 adsorption and TEM, and have been tested in the asymmetric hydrogenation of two different substrates: methyl 2-acetamidoacrylate and α-acetamidocinnamic acid. The hybrid nanocatalysts have shown to be active and enantioselective in the hydrogenation of α-acetamidocinnamic acid. A good recyclability of the catalysts with low leaching and without loss of activity and enantioselectivity was observed.

Annotated bibliography on ruthenium, rhodium and iridium as catalysts; selected references with abstracts, 1881 to June, 1959.

Mode of access: Internet.

Uber das verhalten von anoden aus iridium, platin und rhodium b...

Thesis (doctoral)--

Efficient 1,4-addition of enones and boronic acids catalyzed by a Ni-Zn hydroxyl double salt-intercalated anionic rhodium(III) complex

Intercalation of an in situ prepared [Rh(OH)6]3- complex into an anion exchangeable Ni-Zn layered hydroxy double salt (Rh/NiZn) was demonstrated. The resulting Rh/NiZn effectively catalyzed the 1,4-addition of diverse enones and phenylboronic acids to their corresponding β-substituted carbonyl compounds. In the case of 2-cyclohexen-1-one and phenylboronic acid, a turnover frequency (TOF) of 920 h-1 based on Rh was achieved. The [Rh(OH)6]3- complex maintained its original monomeric trivalent state within the NiZn interlayer following catalysis, attributable to a strong electrostatic interaction between the NiZn host and anionic Rh(III) complex.

Hydrophenylation of internal alkynes with boronic acids catalysed by a Ni–Zn hydroxy double salt-intercalated anionic rhodium(III) complex

[Rh(OH)6]3− intercalated Ni–Zn mixed basic salt (Rh/NiZn) acts as an efficient catalyst for the hydrophenylation of internal alkynes with arylboronic acids under mild conditions. The turnover number per Rh site approached 740 in the reaction between 4-octyne and phenylboronic acid. The catalytic monomeric Rh(III) complex is stabilised within the NiZn interlayers, attributable to a strong electrostatic interaction, promoting its re-use.

Rhodium-catalysed enantioselective C-H functionalization in asymmetric synthesis

Infrared study of the adsorption of NO, NO2 and CO on Rh/Al2O3 catalysts

Infrared spectra of NO, NO2 and CO adsorbed on Rh/Al2O3 have been recorded in order to identify the role of surface Rh-NO+ species in the reactions of NO and CO on Rh surfaces. Rh-NO+ was generated by thermally activated adsorption of NO, adsorption of NO on oxidised Rh or by adsorption of NO2. The latter also gave adsorbed nitrate on both Rh and the alumina support. In the presence of CO, Rh-NO+ acted as a precursor of the Rh(CO)(NO) mixed surface complex of CO and NO.

Dynamic contrast-enhanced magnetic resonance imaging as a biomarker for the pharmacological response of PTK787/ZK 222584, an inhibitor of the vascular endothelial growth factor receptor tyrosine kinases, in patients with advanced colorectal cancer and liver metastases: Results from two phase I studies

Purpose: PTK787/ZK 222584 (PTK/ZK), an orally active inhibitor of vascular endothelial growth factor (VEGF) receptor tyrosine kinases, inhibits VEGF-mediated angiogenesis. The pharmacodynamic effects of PTK/ZK were evaluated by assessing changes in contrast-enhancement parameters of metastatic liver lesions using dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) in patients with advanced colorectal cancer treated in two ongoing, dose-escalating phase I studies. Patients and Methods: Twenty-six patients had DCE-MRI performed at baseline, day 2, and at the end of each 28-day cycle. Doses of oral PTK/ZK ranged from 50 to 2000 mg once daily. Tumor permeability and vascularity were assessed by calculating the bidirectional transfer constant (Ki). The percentage of baseline Ki (% of baseline Ki) at each time point was compared with pharmacokinetic and clinical end points. Results: A significant negative correlation exists between the % of baseline Ki and increase in PTK/ZK oral dose and plasma levels (P = .01 for oral dose; P = .0001 for area under the plasma concentration curve at day 2). Patients with a best response of stable disease had a significantly greater reduction in Ki at both day 2 and at the end of cycle 1 compared with progressors (mean difference in % of baseline Ki, 47%, P = .004%; and 51%, P = .006; respectively). The difference in % of baseline Ki remained statistically significant after adjusting for baseline WHO performance status. Conclusion: These findings should help to define a biologically active dose of PTK/ZK. These results suggest that DCE-MRI may be a useful biomarker for defining the pharmacological response and dose of angiogenesis inhibitiors, such as PTK/ZK, for further clinical development. © 2003 by American Society of Clinical Oncology.

Ultrafine powders of SrTiO3 from the hydrothermal preparation and their catalytic activity in the photolysis of water

Ultrafine powders of SrTiO3 are prepared at 100–150°C by the hydrothermal method, starting from TiO2·xH2O gel and Sr(OH)2 and H2O-isopropanol mixed solvent as the medium, The X-ray diffractograms of the powder show line broadening. The minimum crystallite size obtained ranges from 5 to 20nm with 20% H2O-80% C3H7OH as the reaction medium, as estimated from X-ray half-peak widths and TEM studies. The electron diffraction results indicate high concentration of lattice defects in these crystallites. The optical spectra of the particle suspensions in water show that the absorption around the band gap is considerably broadened, together with the appearance of maxima in the far ultraviolet. Aqueous suspensions of SrTiO3 powders, as such, do not produce H2 or O2 on UV irradiation. After coating with rhodium, H2 and O2 are evolved on illumination. However, the turn over number of O2 is lower than the stoichiometrically expected values from the corresponding values of H2. No correlation of the photocatalytic activity with surface area is observed. The activity of Rh-SrTiO3 slowly deteriorates with extended period of irradiation.

Enantioselective syntheses of diquinane and (cis, anti, cis)-linear triquinanes

The enantioselective syntheses of diquinane and cis, anti, cis-linear triquinanes, starting from the readily available (S)-campholenaldehyde, employing an intramolecular rhodium carbenoid CH insertion reaction, are described. (C) 2010 Elsevier Ltd. All rights reserved.

An Enantiospecific Approach to the 5-8-5 Tricyclic System of Basmanes

An enantiospecific synthesis of the 5-8-5 tricyclic ring system present in the basmane diterpenes has been accomplished, starting from ethyl 3-isopropyl-2-methylene-1-methylcyclopentane-acetate readily available in five steps from (R)-limonene] employing an RCM reaction for the annulation of cyclooctane and an intramolecular rhodium carbenoid CH insertion reaction for the construction of the cyclopentane ring.