Author's School

Graduate School of Arts & Sciences

Author's Department/Program

Chemistry

Language

English (en)

Date of Award

January 2010

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Chair and Committee

Kevin Moeller

Abstract

Cyclization reactions are a significant pursuit in organic synthesis. Unfortunately, many cyclization reactions are either reductive in nature or redox neutral. This can force post-cyclization manipulations to add functional groups and continue the total synthesis. These additional reactions create excess waste and decrease the efficiency of a synthetic scheme. In these cases, it would be nice to do the cyclization in an oxidative fashion. Oxidative cyclizations have been performed, but are currently limited in nature and scope. One way to address this issue is with the use of organic electrochemistry. Electrochemistry appears to be an ideal choice for initiating oxidative cyclizations because it offers an opportunity to make complex ring skeletons in a one-pot reaction using mild conditions that tolerate a variety of functional groups without the use of a chemical oxidant. With this said, the energy source used to power the electrolysis reaction can be a major drawback to the use of electrochemistry, especially if one considers the sustainability of the process. This thesis work looked at two problems in this area. In the first, we attempted to study tandem oxidative cyclizations by electrochemistry. Three different synthetic routes were taken to produce the substrate needed for the electrolysis reaction. In the end, the studies showed that tandem anodic cyclization reactions do not provide a general strategy to complex products. Second, we examined the use of a solar panel as an alternate energy source to power organic electrolyses. A number of olefin coupling reactions and amide oxidations were studied using the solar panel. Differences in how the electron transfer reaction occurred, chemoselectivity, and current efficiency were examined.

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Permanent URL: http://dx.doi.org/10.7936/K7000041

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