ERA

Download the full-sized PDF of Synthesis of benzo-fused nitrogen heterocycles and substituted benzenesDownload the full-sized PDF

Analytics

Share

Permanent link (DOI): https://doi.org/10.7939/R38Q43

Download

Export to: EndNote  |  Zotero  |  Mendeley

Communities

This file is in the following communities:

Graduate Studies and Research, Faculty of

Collections

This file is in the following collections:

Theses and Dissertations

Synthesis of benzo-fused nitrogen heterocycles and substituted benzenes Open Access

Descriptions

Other title
Subject/Keyword
benzene
radical
aromatization
dihydroindole
cyclization
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Ziffle, Vincent
Supervisor and department
Clive, D. L. J. (Chemistry)
Examining committee member and department
Vederas, J. C. (Chemistry)
Knaus, E. (Faculty Pharmacy and Pharmaceutical Sciences)
Lowary, T. L. (Chemistry)
Dake, G. (Chemistry, University of British Columbia)
Li, L. (Chemistry)
Department
Department of Chemistry
Specialization

Date accepted
2010-02-02T22:03:47Z
Graduation date
2010-06
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
The first chapter of this thesis represents the continued development of a general method for the formation of benzo-fused N-heterocycles by formal radical cyclization onto benzene rings. Important stages in this process involve 1) the copper-mediated coupling of various amino alcohols to protected p-iodophenols, 2) carbamate-protection of the resulting aryl secondary amine to allow the following oxidation step, 3) the oxidative formation of quinone ketals as radical acceptors, 4) the radical cyclization of pendant iodo-radical triggers onto the cross-conjugated ketone, and 5) the subsequent aromatization of the resulting products into benzo-fused N-heterocycles. Various protected 2,3-dihydroindoles—some of which with 2-substitutions—have been synthesized using this methodology. For some examples, it was necessary to repeat the experiments of a previous group member to obtain publication-quality data. The second chapter describes a new methodology for the formation of regioselectively-substituted benzene rings. Various arene species have been synthesized in p-disubstituted, 1,2,4-trisubstituted and 1,2,3,4-tetrasubstituted arrays. Key steps in the methodology include 1) the synthesis of 1,4-diketones by alkylation of various aldehydes and their subsequent reduction and oxidation, 2) addition of organometallic alkenes to 1,4-diketones to form ring closing metathesis (RCM) precursors, and 3) RCM and subsequent aromatization of these cyclized products by double-dehydration to form the desired substituted benzenes. The macrocycle [12]-paracyclophane has also been synthesized using a modified version of the above methodology.
Language
English
DOI
doi:10.7939/R38Q43
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

File Details

Date Uploaded
Date Modified
2014-05-01T00:58:50.450+00:00
Audit Status
Audits have not yet been run on this file.
Characterization
File format: pdf (Portable Document Format)
Mime type: application/pdf
File size: 4149598
Last modified: 2015:10:12 16:48:15-06:00
Filename: Ziffle_Vincent_Spring 2010.pdf
Original checksum: 1316ac70bc49f8d40cb9e27c5f84ea26
Well formed: true
Valid: false
Status message: Invalid page tree node offset=238572
Status message: Outlines contain recursive references.
File title: Final Pref Tues
Activity of users you follow
User Activity Date