Date of Award

7-29-2011

Document Type

Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Justin D. Fair, Ph.D.

Second Advisor

Roberta M. Eddy, Ph.D.

Third Advisor

Carl LeBlond, Ph.D.

Fourth Advisor

John T. Wood, Ph.D.

Fifth Advisor

George Long, Ph.D.

Abstract

This thesis describes the investigation into asymmetric deprotonation of dipole-stabilized α-aminoorganolithiums. The lithiation of N-Boc-N-(3-butenyl)benzylamine provides a configurationally stable organolithium intermediates complexed to an oxygen atom. Preparation of heterocyclic rings is inhibited by this Li-O complex, therefore, restricting cyclization of unsaturated organolithium to form 5-membered rings. However, the protection group on nitrogen plays a crucial role in the reaction topology, as an unexpected rearrangement occurred to provide for products that contained elimination abducts. An apparent 3-exo-trig cyclization occurs, followed by rapid and irreversible fragmentation of the strained 3-membered ring intermediate. This led to the investigation of a variety of different substituent attached to the nitrogen in place of N-Boc. The conditions for the different substituent were probed at various temperature, bases, solvents, and ligands.

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