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dc.contributor.advisor Coltart, Don M en_US
dc.contributor.author Yost, Julianne en_US
dc.date.accessioned 2009-05-01T18:00:24Z
dc.date.available 2011-07-26T04:30:03Z
dc.date.issued 2009 en_US
dc.identifier.uri http://hdl.handle.net/10161/1053
dc.description Dissertation en_US
dc.description.abstract <p>Carbon–carbon bond-forming reactions comprise the most important class of synthetic transformations. The development of improved and simplified approaches to these reactions will make important and useful contributions not only to the field of synthetic organic chemistry, but also to the many other areas of science that rely on it. Enolate based carbon–carbon bond formation is fundamental to synthetic organic chemistry and has provided the foundation for advancement to its present state. Herein, an important aspect of enolate chemistry is explored: the development of direct methods for carbon–carbon bond formation based on soft enolization of thioesters. Both metal-mediated and organocatalytic approaches to soft enolization are described.</p><p>MgBr<sub>2</sub>·OEt<sub>2</sub>-promoted soft enolization conditions were developed and successfully applied to the aldol addition and Mannich reactions, resulting in a mild and efficient direct reaction that is inexpensive and can be used under atmospheric conditions. A conjugate addition approach to chemoselective deprotonation was also explored and applied to the aldol. In addition, the first organocatalytic Mannich reaction based on proximity-accelerated intramolecular soft enolization of thioesters was developed. Given the advantages of soft enolization, including the inherent operational simplicity, and the accessibility of thioesters, we expect these methods to meet with wide application.</p> en_US
dc.format.extent 3329792 bytes
dc.format.mimetype application/pdf
dc.language.iso en_US
dc.subject Chemistry, Organic en_US
dc.subject direct aldol reaction en_US
dc.subject magnesium en_US
dc.subject Mannich reaction en_US
dc.subject organocatalysis en_US
dc.subject soft enolization en_US
dc.subject thioesters en_US
dc.title Leveraging the Reactivity of Thioesters in the Development of New Methods for Carbon–Carbon Bond Formation en_US
dc.type Dissertation en_US
dc.department Chemistry en_US
duke.embargo.months 24 en_US

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