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Permanent link (DOI): https://doi.org/10.7939/R3H72P

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Methodology and natural product synthesis: carbocycles, culpin and sorbicillactone A Open Access

Descriptions

Other title
Subject/Keyword
sorbicillactone A
bismuth trichloride
culpin
desymmetrization
carbocycles
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Sunasee, Rajesh
Supervisor and department
Dr. D. L. J. Clive (Chemistry)
Examining committee member and department
Dr. C. Szymanski (Biological Sciences)
Dr. J. C. Vederas (Chemistry)
Dr. C. Cairo (Chemistry)
Dr. L. Li (Chemistry)
Dr. R. Batey (Chemistry, University of Toronto)
Department
Department of Chemistry
Specialization

Date accepted
2009-10-01T15:12:52Z
Graduation date
2009-11
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
The first chapter of this thesis describes the development of a general method for indirectly effecting radical carbocyclization of an alkyl chain onto an aromatic ring. This process involves a Birch reductive alkylation of aromatic tert-butyl esters, chromium(VI)-mediated oxidation and radical cyclization. The cyclized products are easily aromatized by Saegusa oxidation and treatment with bismuth trichloride. This method forms five- and six-membered benzo-fused carbocycles. Modification allows both formation of non-phenolic products, and the introduction of an additional substituent on the original aromatic ring. The second chapter describes a method for converting tert-butyl benzoates or tert-butyl 1-naphthoates into derivatives having a substituted alkyl group in a 1,4-relationship to an alkyl, aryl, alkenyl or alkynyl group. Key steps in the process involve addition of an organometallic species to a cross-conjugated cyclohexadienone followed by treatment with bismuth trichloride, which results in spontaneous decarboxylative aromatization. The method was successfully applied to the synthesis of the antimicrobial fungal metabolite culpin. The last chapter of this thesis describes synthetic studies towards the marine antileukemic alkaloid, sorbicillactone A. Studies towards the core structure of sorbicillactone A have resulted in a new method of desymmetrization of cross-conjugated cyclohexadienones. The key step involves a highly diastereoselective iodoetherification and radical cyclization, which affords a product that can be elaborated into a γ-lactone.
Language
English
DOI
doi:10.7939/R3H72P
Rights
License granted by Rajesh Sunasee (rsunasee@ualberta.ca) on 2009-09-29T01:25:58Z (GMT): Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of the above terms. The author reserves all other publication and other rights in association with the copyright in the thesis, and except as herein provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
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