Huestis, Malcolm P2013-11-072013-11-0720092009Source: Masters Abstracts International, Volume: 49-03, page: 1833.http://hdl.handle.net/10393/28662http://dx.doi.org/10.20381/ruor-12654The formation of carbon-carbon bonds is the single most fundamentally important operation in synthetic organic chemistry. Arguably, the aldol and Diels-Alder reactions stand as the most significant advances in forging linkages between carbons of an sp3-hybridized nature. Beginning in the early 1970s, seminal advances were made with respect to formation of carbon-carbon bonds between sp2 centers. These transformations, termed "cross-coupling" reactions, have undoubtedly changed the way synthetic organic chemistry is carried out, rendering the synthesis of carbon-carbon sp2 linkages a relatively trivial task. New synthetic technologies that utilize catalytic quantities of transition metals continue to be developed, and have paved the way to enable rapid increases in molecular complexity with far less effort than previously required. The active ingredient in traditional cross-coupling reactions is a catalytic quantity of palladium. Provided that the two reactants to be cross-coupled have the appropriate functional groups for cross-coupling, they bind to the palladium and eliminate together, bound by a covalent Csp2 -Csp2 bond. These functional groups include halides, boronic acids and esters, and organometallic fragments. Direct arylation is a recent advance in cross-coupling between aryl groups whereby one cross-coupling partner (usually the one bearing an organometallic fragment) is replaced by the simple arene (C-H bond). In the first section, we describe our efforts in extending the direct arylation technique to azaindole compounds. Ultimately, this research led to two different palladium-based catalyst systems - one that performed the cross-coupling event on the azine ring of azaindole, and one that arylated the azole ring. In the second section, we extend our work on a cross-coupling technique catalyzed by rhodium, wherein a five-membered azole ring is constructed oxidatively by reaction between an anilide and an alkyne. This reaction finds its precedent in the Larock indole synthesis, a reaction catalyzed by palladium that features the anilide possessing an ortho-iodo function. In the final section, we demonstrate the direct coupling of two unactivated C-H bonds in an intramolecular sense. This methodology was particularly useful for synthesizing carbazoles, and the synthesis of several highly oxygenated, naturally-occurring carbazo1es is described.112 p.enChemistry, Inorganic.Thesis