Recently, organometallic reactions in aqueous media have received considerable attention in organic synthesis because of environmental and economical concerns and synthetic efficiency. In this connection, the synthetic utility of environmentally benign non-toxic bismuth metal for aqueous organometallic reactions is investigated. Bismuth metal activated by ammonium hydrogen fluoride can efficiently reduce a wide variety of alpha-halocarbonyl compounds in aqueous media to provide the corresponding dehalogenated reduction products in excellent yields. Zinc fluoride is also found to be effective in activating bismuth to mediate the crossed aldol type reactions of diverse alpha-bromocarbonyl compounds with aldehydes in aqueous media to afford the corresponding beta-hydroxycarbonyl compounds in moderate to high yields. The scope of bismuth-mediated aqueous organometallic reactions is successfully extended to the Reformatsky type reactions. The factors that affect the reactivity of these reactions are examined and plausible reaction mechanisms are proposed.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.79029 |
| Date | January 2003 |
| Creators | Lee, Yoon Joo, 1974- |
| Contributors | Chan, T. H. (advisor) |
| 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 | Master of Science (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001985119, proquestno: AAIMQ88244, Theses scanned by UMI/ProQuest. |
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