UC Berkeley

Abstract

The Development of Palladium-Catalyzed C-H Oxidation Reactions and Cooperative

Chemoenzymatic Reactions

By

Zachary Charles Litman

Doctor of Philosophy in Chemistry

University of California, Berkeley

Professor John F. Hartwig, Chair

The following dissertation discusses the development and study of palladium-catalyzed C-H

oxidation reactions and cooperative chemoenzymatic reactions.

Chapter 1 provides a summary of methods for the synthesis of anilines and related compounds.

An overview of C-N and C-O bond formation from the reductive elimination of palladium (IV)

complexes is discussed, and the history of allylic C-H acetoxylation is reviewed. A brief

discussion of the types of chemoenzymatic transformations is also included in this chapter.

Chapter 2 describes a palladium-catalyzed amination of arenes to form N-aryl phthalimides with

regioselectivity controlled predominantly by steric effects. The scope and challenges associated

with the development of this reaction are discussed.

Chapter 3 summarizes mechanistic information about the C-H amination of arenes and describes

the synthesis of model complexes to evaluate the possibility of C-N bond formation from the

reductive elimination of a palladium (IV) intermediate.

Chapter 4 describes the development of a palladium-catalyzed oxidation of hindered alkenes to

form linear allylic esters. The scope and the functional group tolerance of this reaction are

discussed in detail.

Chapter 5 describes the development of a new type of cooperative chemoenzymatic system that

combines the photocatalytic isomerization of alkenes with enzymatic reduction to generate

enantioenriched products in high yields and ee’s.