Thesis (M.S.)--University of Texas at El Paso, 2007. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Thesis (Ph. D.)--University of Nevada, Reno, 2007. / "May, 2007." Includes bibliographical references. Online version available on the World Wide Web.

Thesis (Ph. D.)--University of Oregon, 2008. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 131-143). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.

Thesis (Ph. D.)--University of Hong Kong, 1995. / Includes bibliographical references (leaf 320-343).

Thesis--Wisconsin. / Vita. Includes bibliographical references (leaves 270-278).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1982. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Florida, 2000. / Printout. Vita. Includes bibliographical references (leaves 150-156). Also available on the World Wide Web; PDF reader required.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1983. / Typescript. Vita. Includes bibliographical references (leaves 467-476).

M.Sc. / The aim of this project was the synthesis of viridamine analogues, to be used for selective metal complexation. This, therefore, required the synthesis of diketopiperazines, containing an imidazole-type side chain. The imidazole functionality was introduced into the synthesis via peptide acid coupling reaction between histidine and another amino acid. Before any coupling reactions were possible it was necessary to protect the carboxylic acid functionality of one of the two amino acids being used and the amine functionality of the other. This was to prevent mixed products forming. Owing to the continued difficulty at achieving selective N-protection of histidine, it was decided to make use of the corresponding methyl ester instead. After some initial attempts, it was found that the methyl ester of histidine, which was bought as the dihydrochloride salt, could be readily coupled to a variety of Boc protected amino acids. The Boc protected amino acids could be prepared under various conditions using di-tertbutyl dicarbonate. A range of conditions was investigated for the coupling of the two amino acids, i.e. the histidine methyl ester dihydrochloride and a Boc protected amino acid. Successful coupling was finally achieved using tetrahydrofuran as solvent, N-hydroxy benzotriazole as reaction promoter, N-methyl morpholine as a base and dicyclohexylcarbodiimide as the coupling agent. After varying the reaction conditions the optimised reaction conditions gave yields in the region of 76%. Once coupling had been achieved, it remained to cyclise the dipeptide. Cyclisation was preceded by the removal of the Boc protecting group either in situ or in a two step process. In the absence of the imidazole functionality, removal of the Boc group was readily achieved using trifluoroacetic acid. However, attempted deprotection of dipeptides containing the imidazole functionality led to decomposition of the dipeptide under identical conditions. It was therefore necessary to find an alternative form of deprotection. This was found in the form of formic acid, which proved to be successful in removing the Boc group and in effecting cyclisation to the analogous diketopiperazine. This particular form of in situ cyclisation proved to be very low yielding. This problem was circumvented by following the formic acid treatment by a period of reflux in a toluene I 2-butanol mixture. Cyclisation was effected with pure products being obtained in high yield, after column chromatography. Complexation reactions were initiated with the synthesised diketopiperazines but unfortunately no X-Ray diffraction studies could be carried out, due to the formation of amorphous solids instead of crystalline materials.

M.Sc. / There were two main objectives of the research presented m this dissertation. Firstly, the synthesis of bulky electron withdrawing phosphine-alkene ligands for classic ligand testing in the Suzuki cross-coupling reaction was performed. Previously, a range of electron deficient phosphine-alkenes was prepared from 2- ( diphenylphosphino )benzaldehyde, using both Wittig and Knoevenagel chemistry. These were tested for catalysis and gave high yields for the Suzuki reaction. In the present instance, 2-( di-otolylphosphino) benzaldehyde was synthesised making use of Grignard technology from acetyl protected 2-bromobenzaldehyde and chloro(di-o-tolyl)phosphine (itself prepared from PCh. And the appropriate o-tolyl Grignard reagent. This material served as a building block for the generation of P-alkene ligands which were synthesised making use of Wittig, Knoevenagel and transesterification chemistry. These o-tolyl analogues of the P-alkene ligands prepared in the previous study were used in ligand testing experiments in the Pd-catalysed Suzuki cross-coupling reaction. The results of the catalysis showed an enhanced activity with these ligands over the previous cases The second part of this dissertation involved determining the role (influence on activity) of the non coordinating counterion in the catalyst system in the methoxycarbonylation reaction. To this end discrete Pd complexes were synthesised and used directly in the methoxycarbonylation reaction. There have been a few reports on the role of the non-coordinating counterions of the catalyst systems in the methoxycarbonylation reaction. The catalyst is typically a palladium compound in the presence of a Bmnsted acid co-catalyst. Changes to the Bmnsted co-catalyst cause two variables to change, namely the acidity of the acid and the nature of the counterion that the acid provides. The work presented in this dissertation shows the results of only one variable being changed (that of the counterion) and as such allowed the specific role of the counterion in the outcome of the reaction to be determined. Previous work done in our laboratories made use of the Lewis acid Al(OTf)3 to co-catalyse the methoxycarbonylation reaction with rates and high yields being observed. In the present instance discrete Pd complexes were synthesised from Pd(OAc)2 using p-TsOH, MsOH and TfOH as the acids containing the weakly coordinating counterions. These Bnmsted acids have the ability to displace the OAc- anion from the Pd and as such formed the discrete L2PdX2complexes (L = PPh3; X = Mso-, p-Tso-, TfO} Synthesis of these discrete complexes was impeded by a lack of knowledge of the specific conditions under which to prepare the complexes and many avenues were pursued before successful isolation of these complexes was achieved. These discrete catalysts were used in the methoxycarbonylation reaction co-catalysed by Al(OT£)3. Here, the Al(OTt)3 forms the basis of a constant acid cocatalyst allowing only the counterion to be changed with the view to determining its role in these reactions. It was found that the counterion appears to play no role at all (Aco-, p-Tso-, Mso-, TfO-) in the outcomes of these reactions under the conditions employed. A comparative study is also detailed herewithin of the effects of both ex situ and in situ catalyst generation on the activity in the methoxycarbonylation reaction, which provides some insightful results.