No description available.

In order to provide scalable, efficient and selective routes towards pharmaceutically relevant compounds, we have focused on improving the economical viability and practicality of strained-silane Lewis acid activation. Towards these goals, the Leighton group has developed a new mode of anion catalysis to activate silane Lewis acids. Weakly coordinating anions have been used to access hyper-coordinate silicon species with unprecedented levels of reactivity, which have facilitated previously unattainable complex fragment couplings. A highly enantioselective and efficient method for anion catalyzed nucleophilic addition to aldehydes has enabled the synthesis of rationally designed, structurally simplified D-ring modified analogs of spongistatin 1. The completion of a step-economical route towards extremely potent, linker-handle equipped spongistatin 1 analogs and their application to targeted drug delivery will be discussed.

This dissertation presents new approaches towards the asymmetric allylation of the imino and formyl functionalities by using strained silanes as Lewis acids. Here in the Laboratory of Professor James L. Leighton, chiral homoallylic alcohols and amines are considered privileged products given their important role as building blocks in natural product synthesis. The new approaches reported herein are focused on expanding the scope of imine allylation reactions and gaining full synthetic utility of the corresponding homoallylic amine products by means of economic and user-friendly protocols. In addition, the discovery of a novel catalytic and mild approach to the asymmetric allylation of aldehydes will be the focus of discussion at the end of this works. Chapter 1 will give a brief introduction about general concepts in asymmetric allylation of aldehydes and imines as well as in applications of strained silane Lewis acids in these reactions. Chapter 2 will discuss the development of a novel asymmetric allylation method for N-heteroaryl hydrazones and the N-heteroaryl cleavage from the product to unmask the corresponding free amines. Chapter 3 will carry on these studies into different imine activating groups in search for a more general and user-friendly approach towards both allylation and cleavage protocols. Finally, Chapter 3 will discuss the development of a new methodology in which chiral bismuth (III) complexes can catalyze the asymmetric allylation of aldehydes with achiral strained allylsilanes.

The molecular recognition of fluoride and cyanide anions has become an increasingly pertinent objective in research due to the toxicity associated with these anions, as well as their widespread use. Fluoride is commonly added to drinking water and toothpastes to promote dental health, and often used in the treatment of osteoporosis, however, high doses can lead to skeletal fluorosis, an incurable condition. Cyanide is also an extremely toxic anion, which binds to and deactivates the cytochrome-c oxidase enzyme, often leading to fatality. The molecular recognition of these anions in water has proven to be challenging. For fluoride, the anion is small, and thus, efficiently hydrated (?H�hyd = -504 KJ/mol), making its complexation in aqueous environments particularly difficult. In addition to being small and efficiently hydrated like the fluoride anion, cyanide has a pKa(HCN) of 9.3 making its competing protonation in neutral water a further complication. Recent efforts to complex fluoride and cyanide have utilized triarylboranes, which covalently bind the anion. Monofunctional triarylboranes display a high affinity for fluoride with binding constants in the range of 105-106 M-1 in organic solvents, and chelating triarylboranes exhibit markedly higher anion affinities. These species, however, remain challenged in the presence of water. This dissertation focuses on the synthesis and properties of novel Lewis acids designed for the molecular recognition of fluoride or cyanide in aqueous environments. To this end, a group 15 element will be incorporated into a main group Lewis acidcontaining molecule for the purpose of: i) increasing the Lewis acidity of the molecule via incorporation of a cationic group, and ii) increasing the water compatibility of the host. Specifically, a pair of isomeric ammonium boranes has been synthesized. These boranes are selective sensors which selectively bind either fluoride or cyanide anions in water. The study of phosphonium boranes has revealed that the latent Lewis acidity of the phosphonium moiety is capable of aiding triarylboranes in the chelation of small anions. Finally, my research shows that Br�nsted acidic H-bond donors such as amides, when paired with triarylboranes, are capable of forming chelate complexes with fluoride.

The primary goal of the research described in this thesis concern the synthesis, characterization and study of 1,8-bis(diarylmethylium)naphthalenediyl dications. Such dications have been prepared from the corresponding diols and have been fully characterized. Single crystals X-ray diffraction studies indicate that the two cationic centers of these derivatives are separated by 3.0 - 3.1 ??. The enforced proximity of the cationic centers intensifies the electron deficiency of these derivatives which behave as strong organic oxidants. As indicated by cyclic voltammetry, these dications undergo a two-electron reduction to afford the corresponding acenaphthenes. The newly formed C-C bond which links the former methylium are remarkably long (1.628-1.706 ??.) and can, in some instances, be oxidatively cleaved in the presence of acids. These dications can also be reduced chemically by reducing reagent, such as hydride, chloride, bromide and iodide. Remarkably, the reaction of 1,8-bis(diphenylmethylium)naphthalenediyl dication with fluoride anion results in the formation of a mono fluorinated cation which features an unsymmetrical C-F?C bridge between the former methylium centers. As indicated by 1H NMR spectroscopy, the structure of this cation is fluxional with the fluorine atom oscillating between the former methylium centers. Finally, this thesis also deals with the synthesis and study of 4,6-bis(dimesitylboryl)dibenzofuran and isoelectronic dications.

Thesis (Ph. D.)--University of Toledo, 2009. / Typescript. "Submitted as a partial fulfillment of the requirements for the Doctor of Philosophy Degree in Chemistry." Includes bibliographical references (leaves 123-132).

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references. Available also in a digital version from Dissertation Abstracts.

No description available.

Thesis (Ph. D.)--University of Hong Kong, 2008. / Also available in print.

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.