Potassium permanganate oxidations and novel cycloaddition chemistry of the arene-cis-diols (7) were investigated. It was found that permanganate oxidation of arene-cis-diols yielded a mixture of 2 products, (157a) and (157b) in low yield. The influence of the C1-substituent on the outcome of the reaction was found to be a complex mixture of steric and electronic effects. In the area of cycloaddition chemistry of protected (7), this thesis describes novel [4+2] cycloadditions with quinones along with the first published report of benzyne and nitrile oxide cycloadditions of these homochiral molecules. The structure of the cycloadducts were elucidated by nOe as well as 2D-NMR analysis and were supported by Frontier Molecular Orbital theory. Finally, arene-trans-diols (200) were synthesized from (7) by a multistep stereoselective protection/deprotection sequence utilizing the Diels-Alder reaction. These compounds serve as intermediates in an approach to the amaryllidaceae alkaloid (+)-pancratistatin (12). / Ph. D.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/38267 |
| Date | 06 June 2008 |
| Creators | McKibben, Bryan P. |
| Contributors | Chemistry, Hudlicky, Tomas, Tanko, James M., Kingston, David G. I., Merola, Joseph S., Gandour, Richard D. |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Language | English |
| Detected Language | English |
| Type | Dissertation, Text |
| Format | ix, 166 leaves, BTD, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
| Relation | OCLC# 32749118, LD5655.V856_1994.M437.pdf |
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