Reactivity studies of arene-cis-diols in cycloadditions and potassium permanganate oxidations: synthesis of the corresponding arene-trans-diols and an approach to the synthesis of (+)-pancratistatin

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).

Name thesis:degree_name

Ph. D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

1994

Author dc:creator

• McKibben, Bryan P.

Chair dc:contributor.committeechair

• Hudlicky, Tomas

Committee members dc:contributor.committeemember

• Tanko, James M.
• Kingston, David G. I.
• Merola, Joseph S.
• Gandour, Richard D.

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en

Dc Identifier Other

etd-06062008-164317

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/38267