Date of Award
Chemistry and Biochemistry
McIntosh, John M.,
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Part A. The alkylation trans 2-arylcyclohexyl hippurates with a series of electrophiles was examined. The reaction stereoselectivity varied from 46 to 81% depending on the steric and electronic nature of the electrophile when (Ar = phenyl). Higher stereoselectivity was observed when reacting electrophiles of increasing pi-character. When the chiral auxiliary contained a naphthyl group the stereoselectivity was >80% for every electrophile used. Part B. The alkylation of the trans 2-phenylcyclohexylamide of methyl glycinate with a series of electrophiles was examined. Incorporation of the chiral auxiliary on the amino terminus of the amino acid appears to induce good stereoselectivity only when the electrophiles contain a point of unsaturation. The reaction stereoselectivity ranged from 21 to 80% depending on the electronic nature of the electrophiles. It is proposed that a pi-stacking interaction between the aromatic group on the auxiliary and the unsaturated electrophiles was responsible for the high stereochemical excess observed. Source: Masters Abstracts International, Volume: 39-02, page: 0514. Adviser: John M. McIntosh. Thesis (M.Sc.)--University of Windsor (Canada), 1999.
Peters, Scott Owen., "Induced pi-facial discrimination in the alkylation of chiral derivatives of glycine." (1999). Electronic Theses and Dissertations. 2426.