Chemistry, Department of

 

Department of Chemistry: Dissertations, Theses, and Student Research

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First Advisor

Patrick H. Dussault

Date of this Version

12-2012

Document Type

Thesis

Citation

A thesis presented to the faculty of the Graduate College at the University of Nebraska in partial fulfillment of requirements for the degree of Master of Science

Major: Chemistry

Under the supervision of Professor Patrick H. Dussault

Lincoln, Nebraska, December 2012

Comments

Copyright 2012, Benjamin W. Puffer. Used by permission

Abstract

A common reaction to yield ethers relies on an alkoxide nucleophile and a carbon electrophile (Williamson ether formation). Ethers can also be formed by reactions with carbon nucleophiles and oxygen electrophiles by way of the peroxide functional group. We screened a number of carbon nucleophiles suitable for attack on dialkyl peroxides to form new C-O bonds. Also a novel approach using a peroxyketal electrophile is shown to increase the efficiency of this intermolecular reaction. This method of C-O bond formation can also be implemented intramolecularly, not seen before in the literature, to yield cyclic ethers. This approach requires the generation of an organolithium, via lithium/heteroatom exchange, in the presence of a peroxide. The intramolecular C-O bond formation is shown here to yield 5 and 6-membered ethers as well as oxetenes.

Advisor: Patrick H. Dussault

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