The synthesis of 95, a non-hydrolyzable dinucleotide analogue bearing an internucleoside thioether linkage, is described. The 3$ sp prime$-deoxy-3$ sp prime$-C-(2$ sp{ prime prime}$-substituted-ethyl) branched-chain sugar and nucleoside precursors were efficiently prepared from 1,2-O-isopropylidene-$ alpha$- scD-xylofuranose. / In the course of this work, it was found that intramolecular 5,2$ sp prime$-sulfide formation occurs very rapidly, in spite of the trans-fusion of the bicyclic ring system. This enabled the straightforward preparation of the novel perhydro-oxathiahydrindane nucleosides 41 and 43 as well as the cAMP analogue 51. Detailed NMR analysis of the bicyclic compounds was performed. / The acetolytic deacetalation of branched-chain thiosugars 11 and 68 was found to give a variety of non-furanose products, including the novel thiolanes 71 and 74, whose formation was dependent on the reaction temperature. The competing acetolysis mechanisms and the implications on related phenomena are discussed.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.74659 |
| Date | January 1990 |
| Creators | Kawai, Stephen H. |
| 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: 001236402, proquestno: AAINN67771, Theses scanned by UMI/ProQuest. |
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