Bibliography: leaves 167-176. / viii, 176 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / This thesis aims to attach dyes to amino acids in a protein. The study examines the 1,4-addition (Michael type) of the nucleophilic groups present in a protein onto a conjugated alkyne reactive group bound to a dye moiety. The initial studies examine the reactivity of individual amino acids with nucleophilic side chains which are common in proteins towards conjugated alkynes. The second stage of the project requires the synthesis of a series of compounds such as those where a dye is attached to a conjugated alkyne via a spacer unit. The reactivity of these compounds with the individual amino acids is studied, as well as the attachment of compounds of this type to, initially, short peptides, and later to a protein such as wool. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemistry, 1997?

Thesis (M.S.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on January 11, 2008) Includes bibliographical references.

There is no abstract available for this thesis. / Department of Chemistry

Two areas of organotransition metal chemistry and their potential application to organic transformations are discussed. The synthesis of cations of the type [Fe(η⁵-C₅H₅)(L)₂(CO)]⁺, [Fe(η⁵-C₅H₄CH₃)(L)₂(CO)]⁺, [Fe(η⁵-C₅(CH₃)₅)(L)₂(CO)]⁺ (where (L)₂=(CO)₂, (PPh₃)(CO), (PMe₃)(CO), (PPh₃)₂,(diphos) and (PMe₃)₂) and [Mo(η⁵-C₅H₅)(L)₃(CO)] (where (L)₃=(PPh₃)(CO)₂, (diphos)(CO) and (triphos)), many of them novel, is described. Investigations into the site of nucleophilic attack on the cations using hydride as a probe and the effect of varying the overall charge distribution of the cation are discussed. Hydride attack on a carbonyl ligand leads to the formation of metal formyl moieties and their detection by low temperature ¹H n.m.r. spectroscopy is described; furthermore, the fate of the metal formyls was found to be dependent upon the nature of the other ligands in the complex. A new criterion for establishing the stereoselectivity of nucleophilic attack on η⁵-C₅H₅ ligands is proposed. Hydride attack on an η⁵-C₅H₄CH₃ ligand was discovered to be regioselective occurring at the carbon atom alpha to the methyl-bearing carbon. The direct oxidation of alkenes to epoxides by hydrogen peroxide was shown to be catalysed by some of the metal carbonyl cations. The use of organotitanium reagents to convert vic-dibromides and epoxides to alkenes is discussed. (C₅H₅)₂TiCl₂ was shown to catalyse both a sodium amalgam debromination of disubstituted vic-dibromides and a zinc debromination of mono and disubstituted vic-dibromides. The latter reaction was developed into a synthetically useful procedure. Reduction of (C₅H₅)₂TiCl₂ by both sodium amalgam and zinc dust gave reagents which deoxygenated epoxides. Investigations into the regioselectivity and chemoselectivity of these reagents are discussed. During the synthesis of molecules containing both vic-dibromide and epoxide functionalities, a novel cyclisation was discovered which may have relevance to the biosynthesis of certain marine natural products.

Thesis (Ph.D.)--McMaster University, 2005. / Supervisor: William J. Leigh. Includes bibliographical references. Also available online.

Thesis (Ph.D.)--Ohio University, March, 2008. / Abstract only has been uploaded to OhioLINK. Includes bibliographical references (leaves 115-125)

Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 142-150).

At the threshold of the 21st centry, a new set of challenges is defined by the need to develop sustainable means of preparing chemical commodities demanded by society. Hence, such concepts as atom economy, step economy, and 'green chemistry' have become the requirements for the development of synthetic reactions. Hydrogenation is one of the most powerful catalytic methods which successfully satisfy the stated requirements of modern chemistry. Accordingly, catalytic hydrogenation has been tremendously utilized in industrial settings. The profound impact of hydrogenation portended a powerful approach to reductive carbon-carbon bond formation under hydrogenation conditions, resulting in the discovery of the Fischer-Tropsch process and hydroformylation. However, since this discovery, processes have restricted to the incorporation of a single carbon monoxide unit. Even though there are a few seminal contributions, systematic efforts toward the development of hydrogen-mediated carboncarbon bond forming processes beyond hydroformylation have been absent from the literature. In an exciting advance, the Krische group has shown that it is possible to reductively couple two or more organic molecules simply through their exposure to gaseous hydrogen in the presence of a metal catalyst. This finding has led to the development of a broad, new family of hydrogen-mediated C-C bond formation. Herein, related to hydrogen-mediated C-C bond formation, the overview of metal catalyzed intermolecular reductive coupling in the presence of reducing agents such as borane, silane, alane, metal, and hydrogen is presented. Chapter 2 describes systematic approaches to the development of hydrogen-mediated C-C bond formation and successful preliminary results achieved by our research group. Chapters 3 and 4 will describe the further extension of these hydrogen-mediated C-C bond formations including (1) hydrogen-mediated reductive couplings of conjugated alkynes with iminoacetates, (2) hydrogen-mediated reductive couplings of 1,3-enynes with [alpha]-ketoesters, and (3) hydrogen-mediated multicomponent reductive couplings. The development of catalytic systems for the nucleophilic activation of enones using phosphine catalysts has received attractive attention. Recently, an intramolecular variant of the Rauhut-Currier reaction was developed in our lab. To further extend nucleophilic phosphine catalysis, we have sought to develop new catalytic methodology via phosphine conjugate addition. Chapter 5 describes two new methodologies related to their area: (1) catalytic cycloallylation via nucleophilic phosphine catalysis and (2) allylic amination of Morita-Baylis-Hillman acetates. / text

The kinetic substitution reactions of two different sets of mononuclear Platinum(II) complexes with heterocyclic bio-relevant azole nucleophiles, viz. Imidazole (Im), 1-methylimidazole (MIm), 1,2-Dimethylimidazole (DIm), 1,2,4-triazole (Trz) and pyrazole (Pyz). All substitution reactions were studied under pseudo-first order conditions as a function of the incoming nucleophiles concentration and temperature using stopped-flow techniques and UV/Visible spectroscopy. The first set of complexes included the tridentate polypyridine complexes, Pt(II)(2,2:6,2″-terpyridine)Cl]Cl.2H2O, (PtL1) Pt(II)(1,3-di(2-pyridyl)benzene)Cl, (PtL2) Pt(II)(2,6-di-(2’-quinolinyl)pyridine)Cl](Cl), (PtL3) and Pt(II)(1,3-di-(2’-quinolinyl)benzene)Cl (PtL4). The substitution of these complexes with the previously mentioned azoles showed that tuning electronic communication of the Pt(II) centre towards substitution through quinoline moieties has an opposed effect to that obtained through pyridine moieties, and verified that the trans-effect of a phenyl ring is much greater than that of a pyridine ring. The reactivity trend among the complexes was PtL2 > PtL4 > PtL1 > PtL3. Once the nucleophiles were categorised into two groups based on their structural similarities, reactivity trend observed amongst the nucleophiles was generally Im > Pyz > Trz, based on the basicity (electronic effects) and MIm > Im > DIm based on steric effects. The second series of complexes were tridentate [Pt(bis(2-pyridylmethyl)amine)OH2](ClO4)2, Ptdpa and [Pt(bis(2-pyridylmethyl)sulfide)OH2](ClO4)2, Ptdps of which the kinetics were studies in an aqua medium and at constant ionic strength (0.1 M). Ptdps was found to be more reactive (three magnitude higher) than Ptdpa. The rate of substitution of the aqua ligand is dependent on the strength of the σ-donor character and the π-acceptability of the atom situated trans to the leaving group. The observed reactivity for the azoles followed the trend, MIm > Im > DIm > Trz > Pyz. This reactivity trend is in accordance with the basicity, and reflects steric and electrophilic effects of the nucleophiles. This was supported by DFT calculations and the X-ray crystal structure of Ptdps_Cl. For all substitution reactions, the temperature dependent studies showed an associative activation. It is envisaged that the findings of this project will provide useful information for designing new drugs as part of a protracted search of effective anticancer drugs with a wider spectrum. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2014.

Thesis (Ph. D.)--State University of New York at Binghamton, Department of Chemistry, 2009. / Includes bibliographical references.