Recent years have witnessed a tremendous growth in the number of gold-catalyzed highly selective chemical transformations. The aim of this study was to develop new gold catalytic methods to mediate carbon-carbon, carbon-oxygen and carbon-nitrogen bond forming reactions. / Chapter 2 describes new annulations catalyzed by gold(I) of simple o-hydroxyaldehydes with alkynes. This annulation efficiently generates isoflavanone-type structures, which have many possible applications in the synthesis of isoflavanone natural products. This chapter details the development and the optimization of the reaction conditions. The annulation was applied to various aldehydes and arylalkynes with good efficiency. Furthermore, it incorporated all atoms of both starting materials into the product and thus has a theoretical atom economy of 100%. / Chapter 3 extends the scope of the annulations developed in Chapter 2. Indeed, 2,3-dihydro-1-tosylquinolin-3(1H)-one derivatives, aza-isoflavanones, have been efficiently synthesized via a gold-catalyzed annulation of 2-tosylaminobenzaldehyde and alkynes. The annulation was applied to various arylalkynes with good efficiency. This annulation can be used for the synthesis of a range of potentially bioactive molecules. / Chapter 4 describes applications in the total synthesis of the annulation developed in chapter 2. (+/-)-Pterocarpan and analogues have been efficiently synthesized via the annulation of salicylaldehydes and o-methoxymethoxylphenylacetylene followed by a one-pot reduction and acidic cyclization of the ketones. In addition, isoflavone derivatives have been synthesized rapidly via the annulation of salicylaldehyde and arylacetylenes followed by IBX/DMSO oxidation of the isoflavanones. / As part of our ongoing studies on metal-catalyzed atom economical reactions, the gold/silver-catalyzed addition of arenes to mono-substituted allene, generate exclusive terminal addition products are described in Chapter 5. / Finally, Appendix A explores the use of commercially available polymer-supported triphenylphosphine as a catalyst for the efficient gamma-addition of methyl 2-butynoate with various pronucleophiles. In addition, optimization studies shows no need of a co-catalyst for the reaction in the presence of a mixture of water:toluene (5:1). The polymer-supported triphenylphosphine is recoverable and can be reused efficiently. This gamma-addition is highly atom-economical and the reaction time was reduced under microwave irradiation.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.111900 |
| Date | January 2008 |
| Creators | Skouta, Rachid. |
| Publisher | McGill University |
| 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 | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 002769127, proquestno: AAINR50999, Theses scanned by UMI/ProQuest. |
Page generated in 0.0018 seconds