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The synthesis of chiral organosul fur and phosphorus compounds /

A general route to optically active organosulfur and phosphorus compounds was investigated. Sulfinimides incorporating camphorimide were synthesized directly from a sulfinyl chloride and N-(trimethylsilyl)camphorimide. The diastereomers were found to be inseparable by crystallization or chromatography, although in one case an optically active sulfinamide was prepared by an asymmetric synthesis. / The phosphorus-imide bond was formed by coupling of an asymmetric phosphinous chloride and N-(trimethylsilyl)camphorimide. Addition of sulfur gave N-(phosphinothioyl)camphorimides as separable diastereomers. These were converted into optically active thiophosphoryl compounds which were chiral only at phosphorus. The absolute configurations of the diastereomers were obtained by single-crystal X-ray analysis, through NMR techniques and by conversion into phosphinothioic acids. / Displacement of camphorimide was effected with organometallic reagents, alcohols and thiols to give optically active phosphine sulfides, phosphinothionates and phosphinodithioates respectively. Optical yields of the products were dependant on the reagents and reaction conditions used. Mechanistic rationales are presented to account for the stereochemical results.

Identiferoai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.68563
Date January 1980
CreatorsFriedlander, Barry Terence.
PublisherMcGill University
Source SetsLibrary and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada
LanguageEnglish
Detected LanguageEnglish
TypeElectronic Thesis or Dissertation
Formatapplication/pdf
CoverageDoctor of Philosophy (Department of Chemistry)
RightsAll items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated.
Relationalephsysno: 000127665, proquestno: AAINK51956, Theses scanned by UMI/ProQuest.

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