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Permanent link (DOI): https://doi.org/10.7939/R3RH4C

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New Investigations in the Interrupted Nazarov Reaction Open Access

Descriptions

Other title
Subject/Keyword
Cycloaddition
Electrocyclization
Methodology
Synthesis
Nazarov
Azides
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Scadeng, Owen
Supervisor and department
West, Frederick G. (Chemistry)
Examining committee member and department
Rivard, Eric (chemistry)
Stryker, Jeffrey M (chemistry)
Aube, Jeffrey (chemistry, University of Kansas)
Lowary, Todd L. (chemistry)
Department
Department of Chemistry
Specialization

Date accepted
2014-08-26T09:42:34Z
Graduation date
2014-11
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
The five-membered carbocycle is a structural motif found in a plethora of natural products and bioactive compounds. The Nazarov reaction has emerged as an effective method to synthesize cyclopentenones and acts as a tool for adding structural complexity to molecular frameworks. This dissertation will discuss several projects involving the Nazarov cyclization and its use to build functionality to the cyclopentanoid framework. Chapter 1 provides a detailed recount of recent advances in Nazarov chemistry. Focus on methods to induce enantioselectivity, the use of alternative substrates as Nazarov reaction precursors, and the use of the Nazarov reaction in total synthesis is presented. Chapter 2 describes the formation of bridged bicyclic compounds via a [3+3]-cycloaddition between organoazides and the Nazarov intermediate. These cycloadducts were also found to thermally decompose to produce ring-enlarged dihydropyridones and 6-methylenepiperidinones. In Chapter 3, details the attempted development of a domino Nazarov cyclization/Baeyer-Villiger oxidation are provided. While the desired 3,4-dihydropyra-2-one was formed with the use of bis(trimethylsilyl)peroxide as the oxidant, optimization of the transformation failed to produce synthetically useful yields. Chapter 4 divulges the findings of Nazarov cyclizations of 2-hydroxyalkyl-1,4-diene-3-ones. Originally proposed as substrates that could undergo domino Nazarov cyclization/semipinacol rearrangements, these compounds were found to readily produce alkylidene cyclopentenones under Lewis acid conditions. These substrates provided insight into the effect that 2-hydroxyalkyl substituents have on the charge density of the oxyallyl cation intermediate of the Nazarov reaction and subsequent alkene formation.
Language
English
DOI
doi:10.7939/R3RH4C
Rights
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 author's prior written permission.
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