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Date Permissions Signed

5-29-2020

Date of Award

Spring 2020

Document Type

Masters Thesis

Department or Program Affiliation

Chemistry

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

O'Neil, Gregory (Gregory W.)

Second Advisor

Vyvyan, James R.

Third Advisor

Gilbertson, John D.

Abstract

Herein we report results from experiments aimed at better understanding SmI2(H2O)n reductions of allylic benzoates adjacent to a trisubstituted alkene. When flanked by both a chelating group and stereodirecting group, these reactions can occur with complete regioselectivity and good diastereoselectivity (up to 90:10). Initial experiments suggested that the reaction was stereospecific to alkene geometry. However, further experimentation has revealed that the alkene stereospecificity is substrate dependent. For instance, if the geminal alkene substituents are alkyl, results show the reaction to be stereospecific, but if one of the substituents is a phenyl group the reaction is still stereoselective but not stereospecific. This was demonstrated through the synthesis and subsequent SmI2(H2O)n reduction of a series of cis- and trans-allylic benzoate isomers followed by careful analysis of the product mixtures by 1H NMR. To explain these results our current working hypothesis is based on formation of an η3-organosamarium bicyclic intermediate. In some cases, C-C bond rotation in the pi-allyl intermediate relieves steric strain, leading to a loss in stereospecificity.

Type

Text

Keywords

allyl, organosamarium, stereospecific, stereoselective

Publisher

Western Washington University

OCLC Number

1156472034

Subject – LCSH

Samarium; Acrolein; Benzoates; Reduction (Chemistry)

Format

application/pdf

Genre/Form

masters theses

Language

English

Rights

Copying of this document in whole or in part is allowable only for scholarly purposes. It is understood, however, that any copying or publication of this document for commercial purposes, or for financial gain, shall not be allowed without the author’s written permission.

Available for download on Friday, January 01, 2021

Included in

Chemistry Commons

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