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Date Permissions Signed

5-1-2011

Date of Award

2011

Document Type

Masters Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Vyvyan, James R.

Second Advisor

Peyron, Mark

Third Advisor

Clark, Timothy B. (Chemist)

Abstract

Gold catalyzed reactions are an active area of interest for synthetic chemists due to gold's ability to promote formation of carbon-carbon bonds. A mechanistic study of the aromatic Claisen rearrangement of allyl aryl ethers in the presence of a gold catalyst has shed some light on the role of the gold catalyst in this reaction. Studies probing the electronics requirements of the reaction as well as investigation of stereochemical conservation both support a dissociative ionic mechanism. Our data supports that the catalyst interacts primarily with the alkene branch as opposed to the phenoxide oxygen because the E and Z allyl aryl ether diastereomers form different ratios of the [3,3] and [1,3] rearrangement products. NMR studies have caused us to question our presumed active catalyst, Ph3PAuOTf, and we now suspect gold nanoparticles or a thin gold film are catalyzing the rearrangement. Through investigations of the synthetic scope of our gold catalyst, some unexpected reaction products were produced. A cyclic ether formed when the allyl branch contained an acetonide protecting group. This cyclization was even more effective when the acetonide was first converted to the corresponding diol. This cyclic ether formation was put to practical use in the total synthesis of the natural product (±)-centrolobine.

Type

Text

Publisher

Western Washington University

OCLC Number

729384395

Digital Format

application/pdf

Genre/Form

Academic theses

Language

English

Rights

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

Included in

Chemistry Commons

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