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New Methods for the α-Functionalization of Thioesters and Activated Hydrazones and an Application Toward the Total Synthesis of Apratoxin D

dc.contributor.advisor Coltart, Don M
dc.contributor.author Tarsis, Emily Michelle
dc.date.accessioned 2011-01-06T16:00:37Z
dc.date.available 2012-12-12T05:30:13Z
dc.date.issued 2010
dc.identifier.uri https://hdl.handle.net/10161/3074
dc.description.abstract <p>Cascade reactions, also referred to as domino reactions, have been widely used for the formation of carbon-carbon bonds. This type of reaction has the potential to circumvent protection and deprotection steps, shortening an overall synthetic process.</p><p>The Morita-Baylis-Hillman (MBH) reaction is a particularly notable example of an anionic domino reaction which provides straightforward access to &#946;'-hydroxy-&#945;,&#946;-unsaturated carbonyl compounds from aldehydes and &#945;,&#946;-unsaturated carbonyls. However, despite the importance of the Baylis-Hillman reaction, it is slow, reaction yields are quite low, and the process is not general, as it rarely works for &#946;-substituted &#945;,&#946;-unsaturated carbonyl species. Herein, we report an alternative approach to the preparation of MBH adducts employing an anti-selective direct aldol cascade reaction followed by oxidative elimination. This alternative process is rapid, efficient, and generally applicable, even to &#946;-substituted &#945;,&#946;-unsaturated compounds. </p><p>Progress toward the asymmetric total synthesis of apratoxin D is described. The key step of the synthesis is the asymmetric &#945;,&#945;-bisalkylation of chiral N-amino cyclic carbamate (ACC) hydrazones, a new methodology developed by our group. Herein we demonstrate the utility of this method for convergent total syntheses.</p>
dc.subject Organic Chemistry
dc.subject
dc.title New Methods for the &#945;-Functionalization of Thioesters and Activated Hydrazones and an Application Toward the Total Synthesis of Apratoxin D
dc.type Dissertation
dc.department Chemistry
duke.embargo.months 24


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