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Unconventional Substrates for the Nazarov and Imino-Nazarov Reactions Open Access

Descriptions

Other title
Subject/Keyword
Nazarov reaction
Imino-Nazarov reaction
Friedel-Crafts cyclization
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Bonderoff, Sara A
Supervisor and department
West, Frederick (Chemistry)
Examining committee member and department
Frontier, Alison (Chemistry)
Klobukowski, Mariusz (Chemistry)
Choi, Philip (Chemical and Materials Engineering)
Hall, Dennis (Chemistry)
Clive, Derrick (Chemistry)
Department
Department of Chemistry
Specialization

Date accepted
2012-09-28T07:23:05Z
Graduation date
2012-09
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
5-Membered carbocycles are ubiquitous in natural products and synthetic drugs. Methods of generating them are therefore valuable, and the ability to do so in a stereospecific and enantioselective manner while making considerable gains in molecular complexity with additional incorporation of versatile handles for further elaboration are even more desirable. In the Nazarov reaction, activation of a dienone by a strong Brønsted or Lewis acid results in the formation of a conjugated pentadienyl cation, which can then undergo conrotatory 4π-electrocyclization to yield a cyclopentenone. Recent activity in the area of Nazarov chemistry is summarized in Chapter 1. Unconventional substrates are gaining popularity in the Nazarov field due to their potential to eliminate some of the restrictions faced when using the traditional substrates (divinyl ketones). Chapter 2 describes the preparation of 1-alkoxy-2,2-dichloro-1-vinylcyclopropanes, and their application to the Nazarov cyclization. These compounds undergo electrocyclic ring opening of the cyclopropane followed by Nazarov cyclization to furnish chlorinated 2-cyclopentenones. Importantly, this reaction could be done under catalysis by indium(III) chloride in leading examples. Arene traps were tethered through the akoxy-substituent in an effort to effect a novel mode of interrupted Nazarov reaction; however, this reaction was not realized. During the study of 1-alkoxy-2,2-dichloro-2-vinylcyclopropanes, an unexpected Friedel-Crafts cyclization was observed in some substrates. On further investigation of the process (Chapter 3), it was found that silver(I) bis(trifluoromethanesulfonyl)imide acts as a precatalyst in a Brønsted acid catalyzed intramolecular Friedel-Crafts alkylation of arenes with unactivated alkenes. Electron-rich and electron-deficient arenes as well as heteroaromatic rings reacted with alkenes to afford 5-,6-,7- and 8-membered rings, often generating a quaternary center adjacent to the arene. In stark contrast to the Nazarov reaction, there is very little knowledge about its nitrogen analogue, the imino-Nazarov reaction. In Chapter 4, our approach to the imino-Nazarov reaction of 1-amino-2,2-dichloro-1-vinylcyclopropanes is reported. The cyclization product is a cyclopenteniminium salt, which is reduced to furnish cis-3-amino-4-chlorocyclopentenes. This is the first example of an imino-Nazarov reaction with an electron-rich amine that is retained in the product. These substrates have also afforded the first interrupted imino-Nazarov reaction.
Language
English
DOI
doi:10.7939/R3WM4N
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.
Citation for previous publication
Bonderoff, S. A.; West, F. G.; Tremblay, M. Tetrahedron Lett. 2012, 53, 4600.

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