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Title: Reactions of the dimethylphenylsilyllithium reagent with tertiary amides
Author: Buswell, M.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2002
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Chapter one describes the known reactions of simple, N,N-dimethylamides with phenyldimethylsilyllithium, which give acylsilanes, enediamines or α-silylamines, depending upon the stoichiometry and reaction conditions. This thesis describes five investigations into the scope of these reactions with other amides. Chapter two describes reactions of the acyclic N-phenyl amides A1, which gave the corresponding disilylalcohol A3, presumably by way of the acylsilane A2. (Fig. 1359A). Chapter three describes reactions of N,N-dimethylthioamides A4 with phenyldimethylsilyllithium, which gave enethiols A6 (the more stale tautomer of the thioacylsilane A5). This route is comparable to the known method, which effectively reverses the order of these two steps. (Fig. 1359B). Chapter four describes the synthesis of the silapiperidine protected amides A7 designed to have a protecting group on nitrogen. Reaction wtih the dimethylphenylsilyllithium reagent gave the enediamine A9 and the α-silylamine A8, but the protecting group could not be removed. (Fig. 1359C). Chapter five describes the reactions of N-phenyl-2-pyrrolidinone A10 with phenyldimethylsilyllithium under a variety of conditions giving the products A11 to A17. These represent some remarkable transformations. The stereochemistry of the two tetracyclic dimers A11 and A12 was confirmed by obtaining an X-ray crystal structure. Some aspects of the reaction pathways have been investigated. (Fig. 1359D). Chapter six describes the reactions of some lactams and amides with the phenyldimethylsilyllithium reagent; 1-phenyl-azetidin-2-one, 1-phenyl-piperidin-2-one, 1,3-dimethyl-1,3-dihydro-benzoimidazol-2-one and 1-methylpyridin-2-one.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available