Mild and efficient copper-catalyzed N-arylation of alkylamines and N-H heterocycles using an oxime-phosphine oxide ligand

A mild and efficient copper-catalyzed system for N-arylation of alkylamines and N-H heterocycles with aryl iodides using a novel, readily prepared and highly stable oxime-functionalized phosphine oxide ligand was developed. The coupling reactions could even be performed in solvent-free conditions with moderate to good yields. (c) 2005 Elsevier Ltd. All rights reserved.

Highly efficient copper-catalyzed N-arylation of alkylamines with aryl iodides using phosphoramidite as ligand

A mild and highly efficient copper-catalyzed system for N-arylation of alkylamines with aryl iodides using binaphthol-based phosphoramidites as ligands was developed. The phosphoramidite ligands are stable, cost-effective and easily prepared from inexpensive, commercially available starting materials using a simple, efficient method. (c) 2005 Elsevier B.V. All rights reserved.

Liquid phase oxidation of toluene to benzaldehyde with molecular oxygen over copper-based heterogeneous catalysts

We conducted the liquid phase oxidation of toluene with molecular oxygen over heterogeneous catalysts of copper-based binary metal oxides. Among the copper-based binary metal oxides, iron-copper binary oxide (Fe/Cu = 0.3 atomic ratio) was found to be the best catalyst. In the presence of pyridine, overoxidation of benzaldehyde to benzoic acid was partially prevented. As a result, highly selective formation of benzaldehyde (86% selectivity) was observed after 2 h of reaction (7% conversion of toluene) at 463 K and 1.0 MPa of oxygen atmosphere in the presence of pyridine. These catalytic performances were similar or better than those in the gas phase oxidation of toluene at reaction temperatures higher than 473 K and under 0.5-2.5 MPa. It was suggested from competitive adsorption measurements that pyridine could reduce the adsorption of benzaldehyde. At a long reaction time of 4 It, the conversion increased to 25% and benzoic acid became the predominant reaction product (72% selectivity) in the absence of pyridine. The yield of benzoic acid was higher than that in the Snia-Viscosa process, which requires corrosive halogen ions and acidic solvents in the homogeneous reaction media. The catalyst was easily recycled by simple filtration and reusable after washing and drying.

Factors influencing the catalytic activity of SBA-15-supported copper nanoparticles in CO oxidation

Copper nanoparticles were deposited onto mesoporous SBA-15 support via two different routes: post-grafting method and incipient wet impregnation method. Both XRD and TEM reveal that the post-grafting can make Cu particles very small in size and highly dispersed into channels of SBA-15, while the impregnation method mainly forms large Cu particles on the external surface of SBA-15. TPR experiments show that CuO species formed by the post-grafting method is more reducible than that prepared by the impregnation method. The catalytic activity tests for CO oxidation manifests that the sample prepared by the post-grafting method has a much higher activity than that prepared by the impregnation method, with a lowering of 50 degrees C for T-50, showing a strong dependence of catalytic activity on the size and dispersion of Cu particles. Besides the preparation procedure, other factors including calcination temperature, reduction treatment, copper loading as well as the feed composition, have an important effect on the catalytic activity. The best performance was obtained when the catalyst was calcined at 500 degrees C and reduced at 550 degrees C. The calcination and reduction treatment at high temperature have been found to be necessary to completely remove the organic residue and to generate active metallic copper particles. (c) 2005 Elsevier B.V. All rights reserved.

Effects of High Dissolved Inorganic and Organic Carbon Availability on the Physiology of the Hard Coral Acropora millepora from the Great Barrier Reef

Coral reefs are facing major global and local threats due to climate change-induced increases in dissolved inorganic carbon (DIC) and because of land-derived increases in organic and inorganic nutrients. Recent research revealed that high availability of labile dissolved organic carbon (DOC) negatively affects scleractinian corals. Studies on the interplay of these factors, however, are lacking, but urgently needed to understand coral reef functioning under present and near future conditions. This experimental study investigated the individual and combined effects of ambient and high DIC (pCO2 403 μatm/ pHTotal 8.2 and 996 μatm/pHTotal 7.8) and DOC (added as Glucose 0 and 294 μmol L-1, background DOC concentration of 83 μmol L-1) availability on the physiology (net and gross photosynthesis, respiration, dark and light calcification, and growth) of the scleractinian coral Acropora millepora (Ehrenberg, 1834) from the Great Barrier Reef over a 16 day interval. High DIC availability did not affect photosynthesis, respiration and light calcification, but significantly reduced dark calcification and growth by 50 and 23%, respectively. High DOC availability reduced net and gross photosynthesis by 51% and 39%, respectively, but did not affect respiration. DOC addition did not influence calcification, but significantly increased growth by 42%. Combination of high DIC and high DOC availability did not affect photosynthesis, light calcification, respiration or growth, but significantly decreased dark calcification when compared to both controls and DIC treatments. On the ecosystem level, high DIC concentrations may lead to reduced accretion and growth of reefs dominated by Acropora that under elevated DOC concentrations will likely exhibit reduced primary production rates, ultimately leading to loss of hard substrate and reef erosion. It is therefore important to consider the potential impacts of elevated DOC and DIC simultaneously to assess real world scenarios, as multiple rather than single factors influence key physiological processes in coral reefs.

Analyses of patterns of copper and lead mineralisation in human skeletons excavated from an ancient mining and smelting centre in the Jordanian desert

Grattan, J.P., Al-Saad, Z., Gilbertson, D.D., Karaki, L.O., Pyatt, F.B 2005 Analyses of patterns of copper and lead mineralisation in human skeletons excavated from an ancient mining and smelting centre in the Jordanian desert Mineralogical Magazine. 69(5) 653-666.

Modern Bedouin exposures to copper contamination: an imperial legacy?

Grattan, J. Huxley, S. Pyatt, B. Modern Bedouin exposures to copper contamination: an imperial legacy? Ecotoxicology and environmental safety. 2003. 55 pp 108-115

'Death...more desirable than life'? The human skeletal record and toxicological implications of ancient copper mining and smelting in Wadi Faynan, southwestern Jordan

Grattan, J., Huxley, S., Karaki, L. A., Toland, H., Gilbertson, D., Pyatt, B., Saad, Z. A. (2002). 'Death . . . more desirable than life'? The human skeletal record and toxicological implications of ancient copper mining and smelting in Wadi Faynan, southwestern Jordan. Toxicology and Industrial Health, 18 (6), 297-307.

Geochemical evidence for atmospheric pollution derived from prehistoric copper mining at Copa hill, Cwmystwyth, mid-Wales. UK

Mighall, T. Abrahams, P. Grattan, J. Hayes, D. Timberlake, S. Forsyth, S. Geochemical evidence for atmospheric pollution derived from prehistoric copper mining at Copa Hill, Cwmystwyth, mid-Wales, UK. The Science of the Total Environment. 2002. 292 pp 69-80

The local and global dimensions of metalliferous pollution derived from a reconstruction of an eight thousand year record of copper smelting and mining at a desert-mountain frontier in southern Jordan

Grattan, J.P., Gilbertson, D.D., Hunt, C.O. (2007). The local and global dimensions of metaliferrous air pollution derived from a reconstruction of an 8 thousand year record of copper smelting and mining at a desert-mountain frontier in southern Jordan. Journal of Archaeological Science 34, 83-110

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment

Copper phthalocyanine on InSb(111)A?interface bonding, growth mode and energy band alignment, D.A. Evans, H.J. Steiner, S. Evans, R. Middleton, T.S. Jones, S. Park, T.U. Kampen, D.R.T. Zahn, G. Cabailh and I.T. McGovern, J. Phys.: Condens. Matter, 15, S2729?S2740, (2003)

Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry

Jenkins, Tudor; Brieva, A.C.; Jones, D.G.; Evans, D.A., (2006) 'Internal structure of copper(II)-phthalocyanine thin films on SiO2/Si substrates investigated by grazing incidence x-ray reflectometry', Journal of Applied Physics 99 pp.73504 RAE2008

Investigation of catalyst effects in enantioselective copper- and rhodium-mediated transformations of α-diazocarbonyl compounds

This thesis describes the synthesis and reactivity of a series of α-diazocarbonyl compounds with particular emphasis on the use of copper-bis(oxazoline)-mediated enantioselective C–H insertion reactions leading to enantioenriched cyclopentanone derivatives. Through the use of additives, the enantioselectivity achieved with the copper catalysts for the first time reaches synthetically useful levels (up to 91% ee). Chapter one provides a comprehensive overview of enantioselective C–H insertions with α-diazocarbonyl compounds from the literature. The majority of reports in this section involve rhodium-catalysed systems with limited reports to date of asymmetric C–H insertion reactions in the presence of copper catalysts. Chapter two focuses on the synthesis and C–H insertion reactions of α-diazo-β-keto sulfones leading to α-sulfonyl cyclopentanones as the major product. Detailed investigation of the impact of substrate structure (both the sulfonyl substitutent and the substituent at the site of insertion), the copper source, ligand, counterion, additive and solvent was undertaken to provide an insight into the mechanistic basis for enantiocontrol in the synthetically powerful C–H insertion process and to enable optimisation of enantiocontrol and ligand design. Perhaps the most significant outcome of this work is the enhanced enantioselection achieved through use of additives, substantially improving the synthetic utility of the asymmetric C–H insertion process. In addition to the C–H insertion reaction, mechanistically interesting competing reaction pathways involving hydride transfer are observed. Chapter three reports the extension of the catalyst-additive systems, developed for C–H insertions with α-diazo-β-keto sulfones in chapter two, to C–H insertion in analogous α-diazo-β-keto phosphonate and α-diazo-β-keto ester systems. While similar patterns were seen in terms of ligand effects, the enantiopurities achieved for these reactions were lower than those in the cyclisations with analogous α-diazo-β-keto sulfones. Extension of this methodology to cyclopropanation and oxium ylide formation/[2,3]-sigmatropic rearrangement was also explored. Chapter four contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of chiral stationary phase HPLC analysis and X-ray crystallography are included in the appendix.

Copper-catalysed asymmetric sulfide oxidation

The focus of this thesis is the preparation of enantiopure sulfoxides by means of copper-catalysed asymmetric sulfoxidation, with particular emphasis on the synthesis of aryl benzyl and aryl alkyl sulfoxides. Chapter 1 contains a review of the methods employed for the asymmetric synthesis of sulfoxides, compounds with many applications in stereoselective synthesis and in some cases with pharmaceutical application. Chapter 1 describes asymmetric oxidation, including metal-catalysed, non metal-catalysed and enzyme-catalysed, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Kinetic resolution in oxidation of sulfoxides to the analogous sulfones is also discussed; in certain cases, access to enantioenriched sulfoxides can be achieved via a combination of asymmetric sulfoxidation and complementary kinetic resolution. The design and synthesis of a series of sulfides to enable exploration of the substituent effects of the copper-mediated oxidation was undertaken, and oxidation to the racemic sulfoxides and sulfones to provide reference samples was conducted. Oxidation of the sulfides using copper-Schiff base catalysis was undertaken leading to enantioenriched sulfoxides. The procedure employed is clean, inexpensive, not air-sensitive and utilises aqueous hydrogen peroxide as oxidant. Extensive investigation of the influence of the reaction conditions such as solvent, temperature, copper salt and ligand was undertaken to lead to the optimised conditions. While the direct attachment of one aryl substituent to the sulfide is essential for efficient enantiocontrol, in the case of the second substituent the enantiocontol is dependent on the steric rather than electronic features of the substituent. Significantly, use of naphthyl-substituted sulfides results in excellent enantiocontrol; notably 97% ee, obtained in the oxidation of 2-naphthyl benzyl sulfide, represents the highest enantioselectivity reported to date for a copper-mediated sulfur oxidation. Some insight into the mechanistic features of the copper-mediated sulfur oxidation has been developed based on this work, although further investigation is required to establish the precise nature of the catalytic species responsible for asymmetric sulfur oxidation. Full experimental details, describing the synthesis and structural characterisation, and determination of enantiopurity are included in chapter 3.