Catalysis of Ketene and Ketenimine Reactions.

摘要

In the field of catalysis, enolate chemistry and its related derivatives are of paramount importance and avenues for the development of novel catalytic reactions are continually developing. In recent years this chemistry has seen enormous effects toward multifunctional catalysis, particularly in the area of asymmetric fluorination. While most investigators have focused on bifunctional systems, trifunctional systems more closely resemble nature's catalysts, and the result is often improvement for the specific reaction. In this dissertation is described two separate trifunctional systems that were developed. In addition, a novel Diels-Alder reaction with ketenimines and cyclopentadiene is described.;This thesis can be divided into two parts. The first is the largest and introduces a brief overview of ketene chemistry. Next in this section is the derivatization of natural products by asymmetric, bifunctional fluorination of acid chlorides. After this, the transition from a bifunctional system to a trifunctional system is explored. Finally, a new trifunctional method is developed to exact difluorination of acid chlorides.;The second part of this thesis deals with a natural extension of ketene chemistry into ketenimine chemistry. An introduction to ketenimines is followed by a novel Diels-Alder reaction in which ketenimines are allowed to react with cyclopentadiene to create heterocycles.