The diastereoselective synthesis of phosphorothioates and methylphosphonates has been investigated. It has been found that indole is a good leaving group, and that it can form a stable indolephosphorine and can be stereospecifically substituted by a nucleoside in the presence of DBU. / Chiral indole-oxazaphosphorines 31, 39, 44, 56 were synthesized and their reactivities were investigated. The cyano derivative 56 turned out to be a good chiral precursor in the diastereoselective synthesis of a T-T phosphorothioate dimer 65, with a diastereomeric excess larger than 96%. The reaction of cyano, monomer 63 on solid support was investigated. It was found that alkylphosphonate 64 was obtained as the major product, rather than the expected phosphorothioate 65.* / A novel internucleoside coupling reagent 87 was developed for the synthesis of methylphosphonates, in which the indole group can be replaced by a nucleoside within several minutes in the presence of DBU. Several chiral auxiliaries were tested for the stereoselective synthesis of methylphosphonates. A diastereomerically enriched monoester 104 (66% de) was synthesized.* / *Please refer to dissertation for diagrams.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.35646 |
| Date | January 1998 |
| Creators | Wang, Jian-Chao, 1966- |
| Contributors | Just, George (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: 001642724, proquestno: NQ44623, Theses scanned by UMI/ProQuest. |
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