Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 119-130).

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 154-166).

Thesis (Ph. D.)--University of Washington, 1996. / Vita. Includes bibliographical references (leaves [165]-173).

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2007. / Includes bibliographical references. Also available in electronic version.

M.Sc. / The increasing number of individuals living with the HIV virus and the extensive use of antimicrobial medicines has resulted in an increase in opportunistic infections such as tuberculosis, pneumonia, fungal, and viral diseases. In addiction, the drugs currently in use have short comings such as limited efficacy, cell membrane penetration and side effects. The increasing number of opportunistic infections such as systemic fungal infections and the development of resistance to commonly used drugs have prompted the search for answers by producing new and novel ones. Dithiocarbamates (DTCs) have been a subject of major research in the past decade and a number of these compounds have been prepared. Dithiocarbamates are versatile 1,1-dithiolato ligands with broad pharmacological properties. Coordinating these ligands with metals such as copper and nickel may produce compounds with enhanced biological properties and this can be a basis for novel compounds. On the other hand, triphenylphosphine (PPh3) is a good binding ligand for transition metals. Further functionalization of the DTC metal complexes with triphenylphosphine should produce compounds with potential pharmaceutical applications. In this study, several bioactive starting compounds such as indole, imidazole, cyclopentylamine and cyclohexylamine were used to synthesize DTC ligands and their metal complexes of Ni, Co, Cu and Zn. The ligands were obtained in good yields of 55-87% with the complexes in yields of 35-66%. Triphenylphosphine adducts of the DTC metal complexes were also prepared and the yields obtained were between 35-71%. All the prepared complexes and ligands were characterized by Infrared, UV-Vis spectroscopy and NMR (1H, 13C and 31P) spectroscopy.

No description available.

Organoboron compounds are highly valued synthetic intermediates due to their diverse array of reactivity, which is often utilized in the synthesis of valuable organic molecules. For this reason, there is significant interest in the development of novel borylation protocols, especially those whose products are suitable for further synthetic transformations towards valuable classes of compounds. Research in organoboron synthesis has been geared heavily toward transition metal-catalyzed addition to double and triple bonds, though an increasing number of publications detail transition metal-free borylation techniques involving substrate-mediated activation of a diboron reagent. This dissertation describes the author's contributions to the development of both a transition metal-catalyzed diboration and a transition metal-free protoboration. A transition metal-free diboration of alkynamides is described in Chapter 1 which uses the unsymmetrical, differentially protected diboron reagent, pinBBdan. The method installs both boron moieties in a regio- and stereoselective fashion. The products have synthetic value because they are shown to have chemoselectivity in downstream cross-coupling reactions; chemoselectivity is made possible by to the significant difference in Lewis acidity of the pinacol and diaminonapthalene-protected boron centers. This method allows for facile synthesis of tetrasubstituted alkenes with a set geometry about the double bond. A protoboration of allenes employing a Cu(II) catalyst under aqueous and atmospheric conditions is described. Though Cu(I)-catalyzed allene protoboration is well-described in the literature, this is the first report of an analogous Cu(II)-mediated process. The selectivity of the reaction is ligand-controlled, and moderate to good regioselectivities and yields can be achieved through use of a triphenylphosphine as ligand. The method is an environmentally friendly and facile means by which to borylate a challenging cumulated substrate. / Ph. D. / Organoboron compounds are valuable because of their ability to undergo a wide variety of chemical transformations, and they are often used as intermediates in the synthesis of challenging target molecules. In order for this reactivity to be exploited, methods must exist for the efficient synthesis of the desired boron-containing compound. This dissertation describes the author’s contributions to the development of two new methods by which to synthesize organoboron products. The first method involves installation of two differently ligated boron moieties onto an alkynamide substrate to produce a single, uncommon trans isomer as product. A synthetic application of these diboration products is described. The second method involves installation of a single boron moiety into allenes. Though the same overall transformation has been achieved in the literature with use of highly air-sensitive catalysts and organic solvents, the described method entails use of air-stable CuSO4 as catalyst and water as solvent. Therefore, the method is operationally simple and environmentally friendly relative to previously described methods.

Pure rotational spectra of simple metal carbon clusters that relevant to transition metal synthesis and catalysis have been obtained using Fourier transform microwave (FTMW) techniques combined with millimeter-wave direct-absorption methods. Rotational spectra of metal acetylides (CuCCH, ZnCCH, Li/Na/KCCH, MgCCH, AlCCH, CrCCH), diatomic metal monocarbide (CrC) and T-shape metal dicarbides (YC₂ and ScC₂) were recorded in the 4–650 GHz frequency regime. Measurements of weaker isotoplogues including ⁶⁶ZnCCH, ⁶⁸ZnCCH, Zn¹³C¹³CH, ZnCCD, Li/Na/KCCD, CrCCD, Y¹³C¹²C, Y¹³C¹³C, Sc¹³C¹³C, were also studied to aid in structural determinations. This work is the first study of ZnCCH and ScC₂ by any type of spectroscopic technique. Hyperfine splittings in MgCCH and Li/Na/KCCH have also been resolved and the weak isotoplogues of YC₂ have been measured for the first time. Potential interstellar molecules ScO and FeCN were studied using the FTMW techniques in the 4–62 GHz frequency regime. Spectra of the zinc insertion product ClZnCH₃ were additionally recorded in the 10–30 GHz (FTMW) and 260–296 GHz (direct absorption) frequency ranges, along with weaker isotopologues Cl⁶⁶ZnCH₃ and Cl⁶⁸ZnCH₃. This works is the first measurement of zinc insertion products using the FTMW-DALAS techniques. The data were analyzed implementing an effective Hamiltonian, allowing for accurate spectroscopic parameters to be established. From rotational constants, the molecular geometries were accurately determined. Electronic properties were also assessed, including the degree of covalent vs ionic character in a chemical bond, and the molecular orbital composition. The fundamental physical and chemical properties of these benchmark species were obtained in order to gain insight into their role in larger molecular systems, test theoretical calculations, and, in certain cases, provide accurate rest frequencies for astronomical searches.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

No description available.