Development of new reaction methodologies via transition metal catalyzed bond activation processes.

Abstract

ABSTRACT OF THE DISSERTATION Development of New Reaction Methodologies via Transition Metal Catalyzed Bond Activation Processes By Truong-Giang Hoang Professor Christopher J. Douglas, Advisor Chapter 1. This chapter provides an overview my research. The significance of the study towards the field of organic synthesis and the potential challenges are presented. Some examples of relevant achievements in the field of organic synthesis are presented as well. Chapter 2. Presented herein is the study of the ketone carboacylation process. Literature examples for related C–C sigma bond activation are discussed in detail. The isolation and characterization of a rhodium complex intermediate are presented. A hypothesis for acyl C–O bond activation is discussed. Chapter 3. Presented herein is the development of the rhodium catalyzed intramolecular oxyacylation reaction of alkenes with a quinoline directing group. Literature examples for acyl C–O sigma bond activation are discussed in detail. The reaction optimization, substrate scope investigation and a mechanistic proposal are presented. Chapter 4. Presented herein is the study of the intramolecular oxyacylation reactions of alkenes with new directing groups. The optimization for salicylate ester substrates is presented. Literature examples for phenol-directed hydroacylation reactions are discussed in detail. A preliminary substrate scope investigation and a mechanistic proposal are presented. Chapter 5. Presented herein is the development of a novel aromatic ketone synthesis via a tandem C–O activation/C–H functionalization process. Literature examples for related reactions and mechanisms are discussed in detail. The reaction optimization progress and a mechanistic proposal are presented.