Download the full-sized PDF of Exploring New Aspects of the Nazarov CyclizationDownload the full-sized PDF



Permanent link (DOI):


Export to: EndNote  |  Zotero  |  Mendeley


This file is in the following communities:

Graduate Studies and Research, Faculty of


This file is in the following collections:

Theses and Dissertations

Exploring New Aspects of the Nazarov Cyclization Open Access


Other title
Nazarov reaction
Interrupted Nazarov reaction
Alternative Nazarov reaction
Type of item
Degree grantor
University of Alberta
Author or creator
Wu, Yen-Ku
Supervisor and department
West, F. G. (Chemistry)
Examining committee member and department
Suzuki, Keisuke (Chemistry, Tokyo Institute of Technology)
Lowary, Todd L. (Chemistry)
Campbell, Robert E. (Chemistry)
MacMillan, Andrew M. (Biochemistry)
Clive, Derrick L. J. (Chemistry)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
The five-membered carbocyclic framework is a prevailing structural motif found in natural products and bioactive compounds. Over the years, the Nazarov reaction has been continuously refined as a versatile protocol to access cyclopentanoid products. In this dissertation, several projects built on Nazarov chemistry will be detailed. Recent research activities regarding umpolung reactivity at the carbonyl α-carbon, a relatively underemphasized carbonyl umpolung, is discussed in Chapter 1. The cationic intermediates generated during the Nazarov cyclization have been shown to participate in domino or cascade sequences, thus providing a convenient entry to expeditiously increase molecular complexity from relatively simple precursors. Chapter 2 describes a comprehensive investigation of new bond-forming reactions initiated by the Nazarov reaction wherein umpolung reactivity at the α-carbon of cyclopentanones was achieved through the interception of 2-oxidocyclopentenyl cations derived from the initial electrocyclization with an array of carbon nucleophiles. Alternative substrates to the key pentadienyl cation intermediate in the Nazarov reaction, potentially offering access to unconventional substitution patterns or milder conditions, have recently attracted considerable interest. Chapter 3 discusses the use of vinyl silyloxyallenes, which function as dienone surrogates through Brønsted acid activation, to effect the Nazarov cyclization. Additionally, a novel extension of the vinyl allene version of the Nazarov reaction, involving an interrupted Nazarov reaction employing pendent aromatic traps will be presented. Chapter 4 recounts a novel, two-step, modular synthesis of α-amidoindanones. This process is based upon the Nazarov cyclization of 2-amido-1,4-pentadien-3-ones that were in turn prepared via a novel coupling process between α,β-unsaturated aldehydes and an α-lithiated allenamide. As supported by a deuterium labelling study, the mechanism of the coupling entails sequential carbonyl addition and 1,3-sigmatropic rearrangement.
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
Wu, Y.-K.; Niu, T.; West, F. G.*: “Construction of α-Amido-indanones via Formal Allenamide Hydroacylation/Nazarov Cyclization,” Chem. Commun. 2012, 48, 9186-9188.Wu, Y.-K.; McDonald, R.; West, F. G.*: “Homologous Mukaiyama Reactions via Trapping of the Nazarov Intermediate with Silyloxyalkenes,” Org. Lett. 2011, 13, 3584-3587.Wu, Y.-K.; West, F. G.*: “Brønsted Acid-Mediated Nazarov Cyclization of Vinylallenes,” J. Org. Chem. 2010, 75, 5410-5413.

File Details

Date Uploaded
Date Modified
Audit Status
Audits have not yet been run on this file.
File format: pdf (Portable Document Format)
Mime type: application/pdf
File size: 16485113
Last modified: 2015:10:12 21:21:51-06:00
Filename: Wu_Yen-Ku_Spring 2013.pdf
Original checksum: a72861784754864e81aeb7f6ab7c4c5e
Well formed: true
Valid: true
Status message: File header gives version as 1.4, but catalog dictionary gives version as 1.3
Status message: Too many fonts to report; some fonts omitted. Total fonts = 2995
File title: Title page
File title: Microsoft Word - 0-title page - YKW.doc
File author: Yen-Ku Wu
Page count: 340
Activity of users you follow
User Activity Date