Publication Date

2018

Document Type

Dissertation/Thesis

First Advisor

Gilbert, Thomas M.||Adler, Marc Jordan, 1981-

Degree Name

Ph.D. (Doctor of Philosophy)

Department

Department of Chemistry and Biochemistry

LCSH

Organic chemistry||Chemistry

Abstract

1-Hydrosilatrane is an easily synthesized, stable, solid silane which can be made into an efficient reducing agent in the presence of a Lewis base, by taking advantage of the properties of hypervalent silicon. Due to the simplicity of use and handling, 1-hydrosilatrane has the potential to be an appealing alternative to other more widely used reducing agents. Aromatic and aliphatic ketones were readily reduced with 1-hydrosilatrane in the presence of potassium tert-butoxide. The discovery of diastereoselectivity in the reduction of menthone, a chiral ketone, led to enantioselective reductions of prochiral ketones using chiral Lewis base activators. Enantiomeric excesses of up to 86% were observed. It was also shown that 1-hydrosilatrane could act as a chemoselective reducing agent in the formation of tertiary amines via direct reductive aminations, in the absence of activator or solvent. Attempts were also made to take advantage of the steric properties of silicon protecting groups in meta-directing electrophilic aromatic substitution of phenols, leading to a one-pot synthesis of O-aryl carbamates.

Comments

Advisors: Thomas M. Gilbert; Marc J. Adler.||Committee members: Elizabeth Gaillard; Douglas Klumpp; Carol Thompson.||Includes illustrations.||Includes bibliographical references.

Extent

418 pages

Language

eng

Publisher

Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

Media Type

Text

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