Organolithium methodologies and the asymmetric addition of achiral organomagnesium reagents to prochiral ketones or benzaldehyde

Date of Completion

January 2007

Keywords

Chemistry, Organic

Degree

Ph.D.

Abstract

The outcome of reactions of tert-butyllithium and n-butyllithium with 1-bromo-4-tert-butylbenzene, a representative aryl bromide, and (E)-5-bromo-5-decene, a representative vinyl bromide, in various solvents have been investigated. The lithium-bromine exchange of the aryl bromide may be accomplished cleanly and in high yield at 0°C by appropriate choice of solvent; exchange reactions employing the vinyl bromide are best done at -78°C. ^ The Doering-Moore-Skattøbol reaction performed in the presence of (-)-sparteine was investigated. The resulting allene was generated with moderate enantioselectivity. ^ The ability of enantiopure, nonracemic chiral ligands to affect the asymmetric addition of achiral organomagnesium reagents to prochiral ketones and benzaldehyde was investigated. Several methodologies were examined with moderate success. ^

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