Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003. / Includes bibliographical references. Also available in electronic version. Access restricted to campus users.

Title from title page of PDF (University of Missouri--St. Louis, viewed March 3, 2010). Vita. Includes bibliographical references (p. 109-113).

Thesis (Ph. D.)--University of Hong Kong, 1988.

Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 229-236). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 229-236). Also available on the Internet.

Carbon-carbon bond forming reactions are fundamental transformations for constructing structurally complex organic building blocks, especially in the realm of natural products synthesis. Classical protocols for forming a C-C bond typically require the use of stoichiometrically preformed organometallic reagents, constituting a major drawback for organic synthesis on process scale. Since the emergence of transition metal catalysis in hydrogenation and hydrogenative C-C coupling reactions, atom and step economy have become important considerations in the development of sustainable methods. In the Krische laboratory, our goal is to utilize abundant, renewable feedstocks, so that the reactions can proceed in an efficient and atom-economical manner. Our research focuses on developing new C-C bond forming protocols that transcend the use of stoichiometric, preformed organometallic reagents, in which [pi]-unsaturates can be employed as surrogates to discrete premetallated reagents. Under transition metal catalyzed transfer hydrogenation conditions, alcohols can engage in C-C coupling, avoiding unnecessary redox manipulations prior to carbonyl addition. Stereoselective variants of these reactions are also under extensive investigation to effect stereo-induction by way of chiral motifs found in ligands and counterions. The research presented in this dissertation represents the development of a new class of C-C bond forming transformations useful for constructing synthetic challenging molecules. Development of transfer hydrogenative C-C bond forming reactions in the form of carbonyl additions such as carbonyl allylation, carbonyl propargylation, carbonyl vinylation etc. are discussed in detail. Additionally, these methods avoid the use of stoichiometric chiral allenylmetal, propargylmetal or vinylmetal reagents, respectively, accessing diastereo- and enantioenriched products of carbonyl additions in the absence of stoichiometric organometallic byproducts. By exploiting the atom-economical transfer hydrogenative carbonyl addition protocols using ruthenium and iridium, preparations of important structural motifs that are abundant in natural products, such as allylic alcohols, homoallylic alcohols and homopropargylic alcohols, become more feasible and accessible. / text

With the growing demand for miniaturization of devices and for new materials with useful properties, the use of Chemical Vapor Deposition (CVD) for the manufacture of thin films is receiving growing attention. The synthesis of potentially volatile metal complexes and investigation of their use as CVD precursors is an important part of this process. The research presented addresses several major areas of this process, (i) the identification and synthesis of ligands which can impart volatility to a metal complex, (ii) the synthesis, characterization, and assessment of volatility of metal complexes containing these ligands, and (iii) the full materials characterization of thin films grown with these complexes. The use of trimethylphosphine, bis(trifluoromethyl)pyrazolate, and bis(trifluoromethyl)pyrrolyl ligands have been successfully used to synthesize volatile new complexes of cobalt, rhodium, and nickel, some of which show promise for use as potential CVD precursors. / text

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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