Defense Date

4-29-2003

Availability

Worldwide Access

Submission Type

dissertation

Degree Name

PhD

Department

Chemistry and Biochemistry

School

Bayer School of Natural and Environmental Sciences

Committee Chair

Jeffrey D. Evanseck

Committee Member

Jeffry D. Madura

Committee Member

Bruce Beaver

Committee Member

Daniel Singleton

Keywords

catalysis

Abstract

My Ph.D. dissertation describes three different external influences on pericyclic reactions: (1) ionic liquids, (2) Lewis acids and (3) bis(oxazoline)-Cu(II) complexes. (1) Ionic liquids deliver enhanced rates and endo/exo selectivities on the Diels-Alder reaction. The goal is to establish a firm understanding of the molecular interactions that give rise to the observed rate and selectivity enhancements. In order to accomplish our goal, we have used density functional theory methodology, specifically the Becke three parameter with Lee, Yang and Parr corrections at the 6-31G(d), to describe short-range effects, and have created new force field parameters using CHARMM to allow faster classical computations and explore bulk phase effects. (2) Lewis acids are known to influence strongly the rate, regio, endo/exo, diastereofacial and enantio selectivities of the Diels-Alder reaction. Specifically, asymmetric catalysis using chiral Lewis acids provides a crucial tool in the enantioselective synthesis of chiral organic compounds. Uncovering the differential forces between the ground and transition structures with chiral Lewis acids is a perquisite step towards the creation of more effective enantioselective catalysts. Our efforts focus upon a novel combination of two specific intermolecular interactions between boron Lewis acids and Diels-Alder transition structures. Quantum mechanical calculations along with kinetic isotope effects are used in conjunction to elucidate these specific interactions. (3) Cu(II) functions effectively as a Lewis acidic center that has proven to control the stereoselectivity of a wide range of organic reactions. Specifically, bis(oxazoline) copper(II) complexes operate as enantioselective Lewis acid catalysts for carbocyclic and hetero Diels-Alder reactions. We have used quantum mechanical calculations in order to determine how ligand field strength influences Cu(II) coordination and ultimately the stereoselectivity of organic reactions.

Format

PDF

Language

English

Share

COinS