The diastereoselective synthesis of phosphite triesters and related phosphorothioate triesters and diesters has been investigated, with the goal of synthesizing diastereomerically pure DNA phosphorothioates. / Towards this end, the elaboration of a new heterobicyclic structure, imidazo-oxazaphosphorine such as 56, is reported. This unstable intermediate led to the highly diastereoselective synthesis of simple phosphite triesters upon reaction with various alcohols. / Two new types of sterically hindered chiral oxazaphosphorinanes 135 and 146 were then synthesized from cholesterol and camphor respectively. These structures, derived from $ gamma$-aminoalcohols possessing a tertiary alcohol function, could be isolated and characterized. They revealed very reactive in acidic conditions and led to rearrangements. / Finally, oxazaphosphorinane 188 derived from 1,2-O-isopropylidene-D-xylofuranose, was synthesized and characterized. The introduction of a participating group adjacent to the leaving phosphorothioate group led to the fast release of the phosphorothioate moiety. This new chiral auxiliary was successfully used as a precursor in the diastereoselective synthesis of a T-T phosphorothioate dimer, in a diastereomeric ratio of 28.5:1.* ftn*Please refer to dissertation for diagrams.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.42091 |
| Date | January 1996 |
| Creators | Marsault, Eric. |
| Contributors | Just, G. (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 | 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: 001555639, proquestno: NQ30333, Theses scanned by UMI/ProQuest. |
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