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Part A The application of fluorescence resonance energy transfer to reaction discovery Part B The stereodefined synthesis of tetrasubstituted olefins Flynn, Alison B Chemistry, Organic. In part A, the development of methodology for enantioselective reaction monitoring using Fluorescence Resonance Energy Transfer (FRET) is described. The syntheses of enantiomeric epoxides bearing different fluorescent donors and a phenol that bore fluorescence acceptor were explored.* Part B describes the stereodefined synthesis of tetrasubstituted olefins. 2-Alkynyl esters were selectively converted to E-beta-chloro-alpha-iodo-alpha,beta-unsaturated esters by exposure to Bu4NI in refluxing dichloroethane. These products were produced cleanly, regio- and stereoselectively, and in high yields. The treatment of the same substrates with ICI produced mixtures of isomers. Mechanistic studies indicated that ICI was the most plausible intermediate and that a Bu4NI-ICI complex was likely responsible for the high selectivity observed in the Bu4NI/DCE system.* The Bu4NI/DCE system was shown to be selective for the chlorination of alkenes. The treatment of the same alkenes with ICI returned a mixture of chlorinated and iodochlorinated products. In addition, the Bu4NI/DCE system was chemoselective in substrates bearing both aromatic and olefinic moieties, reacting at the alkenyl functionality exclusively. Exposure of these substrates to ICI produced a mixture of products.* The halogenated olefins produced in the initial study were employed as olefin templates for the formation of tetrasubstituted olefins. Regioselective and stereospecific palladium-catalyzed cross-coupling reactions were employed to incorporate a wide variety of substituents into the highly congested olefins, affording single isomer products in good yields.* *Please refer to dissertation for diagrams. 2013-11-08T16:07:23Z 2013-11-08T16:07:23Z 2007 2007 Thesis Source: Dissertation Abstracts International, Volume: 68-10, Section: B, page: 6665. http://hdl.handle.net/10393/29432 http://dx.doi.org/10.20381/ruor-19745 en 392 p. application/pdf University of Ottawa (Canada)