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-dihydroindolessome of which with 2-substitutionshave 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.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:AEU.10048/1009 |
| Date | 06 1900 |
| Creators | Ziffle, Vincent |
| Contributors | Clive, D. L. J. (Chemistry), Vederas, J. C. (Chemistry), Lowary, T. L. (Chemistry), Li, L. (Chemistry), Knaus, E. (Faculty Pharmacy and Pharmaceutical Sciences), Dake, G. (Chemistry, University of British Columbia) |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | 4149598 bytes, application/pdf |
| Relation | Ziffle, Vincent (2006). http://pubs.acs.org.login.ezproxy.library.ualberta.ca/doi/abs/10.1021/jo7026307?prevSearch=ziffle&searchHistoryKey= |
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