Study of rigid alpha-aminoorganolithiums: I Addition of S,N-acetals to aldehydes II Solution structure of alpha-aminoorganostannanes and 1-azaallylic anion on reactions with chiral lithium amides

Date of Award




Degree Name

Doctor of Philosophy (Ph.D.)



First Committee Member

Robert E. Gawley, Committee Chair


Chapter one. Camphor derived N-(Phenylthiomethyl)-oxazolidinone 28 was lithiated and added to aldehydes in good yields and stereoselectivities. The products were crystalline, allowing facile separation of diastereomers from the product mixture. The mechanism and steric course are analyzed and explained in detail.Chapter two. The "Karplus-like" behavior of N-heterocyclic organostannanes was proved by measuring the vicinal coupling constants of 10 and 11. Also, the solution structure of 2-tributystannylpiperidines was investigated by comparison to 11. The apparent presence of a stereoelectronic effect is presented as a possible contribution to the failure of Sn-Li reactions.Chapter three. The investigation of hydrazones, imines, oxime and oxime ethers in the presence of a chiral lithium amide base is presented. The use of chiral amines 29--31 in the formation of a base to affect stereoselectivity on 1-azaallylic anions is examined. The regioselectivity of these "enolate equivalents" is explained in detail.


Chemistry, Organic

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