Sialic acid has been sought as an excellent candidate for $\sp2$H NMR studies because of its ubiquitous presence at the penultimate non-reducing ends of membrane glycoproteins and glycolipids and because it has been associated with a number of biological and immunological phenomena. Regio- and stereoselectively deuteriated sialyl glycerolipids 1a, 1b and 1c were required for these studies and were synthesized.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE MAI) The first step of the synthetic route developed, involved the synthesis of unlabeled and labeled glycerolipids. The regio- and stereoselective deuterium incorporations in sialic acid and subsequent transformation of the deuteriated sialic acids into their respective glycosyl donors followed. The glycosylation of the glycerolipids with the appropriate glycosyl donors completed the synthesis of the model sialylglycerolipids and prompted further investigations of glycosidation methods for the synthesis of sialyl glycosides. A phase transfer catalysis procedure, particularly useful in the synthesis of thiosialosyl donors, was developed and the applicability of the procedure to produce a wide range of S- and O-sialosyl derivatives was explored. An extensive study of thioglycosylation reactions using a series of thiosialosyl donors, the glycerolipid and various thiophilic promoters resulted in the introduction of the concept of active and latent thiosialosyl donors which concluded the synthetic aspect of this research.
| Identifer | oai:union.ndltd.org:uottawa.ca/oai:ruor.uottawa.ca:10393/6766 |
| Date | January 1994 |
| Creators | Letellier de St-Just, Marie Claire H. |
| Contributors | Roy, Rene, |
| Publisher | University of Ottawa (Canada) |
| Source Sets | Université d’Ottawa |
| Detected Language | English |
| Type | Thesis |
| Format | 192 p. |
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