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Organocatalysts for the asymmetric reduction of aromatic ketimines with trichlorosilane

MacDougall, Kenneth N. (2008) Organocatalysts for the asymmetric reduction of aromatic ketimines with trichlorosilane. PhD thesis, University of Glasgow.

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Abstract

Asymmetric reduction of N-aryl ketimines 189a j, 212, and 213 with trichlorosilane can be catalyzed by new N-methyl L-amino acid-derived Lewis-basic organocatalysts, such as bisamide 197c (10 mol%), in toluene at room temperature with high enantioselectivity (≤92% ee). The structure-reactivity investigation shows that the product configuration is controlled by the nature of the side chain of the catalyst scaffold (e.g., i Pr vs Me, as in 197c and 208c), so that catalysts of the same absolute configuration may induce the formation of the opposite enantiomers of the product. Arene-arene interactions between the catalyst and the incoming imine appear to be the prerequisite for asymmetric induction. This metal-free, organocatalytic protocol is competitive with the traditional, metal-catalyzed methodology.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: organocatalysis, reduction, ketimines, trichlorosilane, synthesis
Subjects: Q Science > QD Chemistry
Colleges/Schools: College of Science and Engineering > School of Chemistry
Supervisor's Name: Kocovsky, Prof. Pavel
Date of Award: 2008
Depositing User: Mr Kenneth N MacDougall
Unique ID: glathesis:2008-123
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 02 Mar 2009
Last Modified: 10 Dec 2012 13:15
URI: http://theses.gla.ac.uk/id/eprint/123

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