Defense Date

11-29-2012

Graduation Date

Spring 2012

Availability

Immediate Access

Submission Type

thesis

Degree Name

MS

Department

Chemistry and Biochemistry

Committee Chair

Fraser Fleming

Committee Member

Tomislave Pintauer

Committee Member

Bruce Beaver

Keywords

Metalated nitriles, NMR, organic chemistry

Abstract

The ultimate goal of organic chemistry is understanding the processes involved in carbon-carbon bond formation. Metalated nitriles are perfectly suited for the regio- and stereospecific creation of sterically congested quaternary centers. These traits are dependent on the metal and the metal's preference for coordination to either the nitrile nitrogen lone pair of electrons or the electron pair of the "anionic" carbon bearing the nitrile. This thesis outlines the structural differences in solution between lithiated, cuprated, and magnesiated nitriles, providing the first such study of magnesiated nitriles. Nuclear magnetic resonance, which has become a powerful tool for a wide variety of structural elucidation, indicates both C- and N- binding modes for magnesium with a high dependence on other functionality present within the nitrile substrate. Carbon-carbon bond formation by the attack of a magnesiated nitrile on an alkene is highly unusual. An intramolecular carbo-magnesiation was serendipitously discovered that involves attack on a terminal alkene followed by addition to the nitrile to give a cyclobutanone. Microwave heating greatly enhances the carbometalation process although the carbometalation has only been achieved in two closely related substrates. Insight into the mechanism was obtained although the reaction scope has not yet been extended to other substrates.

Format

PDF

Language

English

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