Methodology and natural product synthesis: carbocycles, culpin and sorbicillactone AReport as inadecuate




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sorbicillactone A, bismuth trichloride, culpin, desymmetrization, carbocycles

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, chromiumVI-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.





Author: Sunasee, Rajesh

Source: https://era.library.ualberta.ca/


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University of Alberta Methodology and natural product synthesis: carbocycles, culpin and sorbicillactone A by Rajesh Sunasee A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Doctor of Philosophy Chemistry Department ©Rajesh Sunasee Fall 2009 Edmonton, Alberta 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 these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the authors prior written permission. Examining Committee Dr.
D.
L.
J.
Clive, Department of Chemistry Dr.
J.
C.
Vederas, Department of Chemistry Dr.
C.
Cairo, Department of Chemistry Dr.
L.
Li, Department of Chemistry Dr.
C.
Szymanski, Department of Biological Sciences Dr.
R.
Batey, Department of Chemistry, University of Toronto DEDICATED TO MY WIFE USHA 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 tertbutyl 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 c...





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