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