Synthesis of a novel conformationally rigid dimer 106 containing a cyclopropyl-phosphonate linkage is described. A novel 3'-phosphonate building block 105 is synthesized and characterized. During the synthesis of the common precursor 86, unusual base-promoted desilylation of epoxide 80 and vinylselenides 85 and 87 are reported. The instability of the tert-butyldimethylsilyl (TBDMS) and the tert-butyldiphenylsilyl (TBDPS) protecting groups may be attributed to the participation of the uracil C2-oxygen anion. / The synthesis of a number of novel bicyclic phosphonate analogs 92b to 95b is described. / In search of alternate cyclopropanation methods, dimesylate 113 was synthesized and characterized. Dimethyl methyl phosphonate anion treatment produced 2'-keto nucleoside derivative 114. The synthesis of a novel reactive epoxide equivalent, the 2 ',3'-cyclic sulfate 119, is described. Dimethyl methylphosphonate anion treatment produced a furane derivative 120 in trace amounts. Reaction of azide anion with cyclic sulfate proceeded regioselectively and gave only 3'-azido nucleoside 122. The observed regioselectivity is novel and may be of great interest to nucleic acid chemists.* / A novel class of galactose and lactose-based glycoconjugates 23 and 24 has been synthesized and fully characterized. During the preparation of these glycoconjugates, novel N-fluorenylmethoxycarbonyl (Fmoc) and N-carboxybenzyl (Cbz)-protected galatosylated and lactosylated linker intermediates 7, 8, 11 and 12 have been synthesized and characterized. / The synthesis of a new active cholane intermediates 19 and 26 is also described.* / *Please refer to dissertation for diagrams.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.34686 |
| Date | January 1997 |
| Creators | Yannopoulos, Constantin G. |
| 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: 001614447, proquestno: NQ37032, Theses scanned by UMI/ProQuest. |
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