The Application of Low Molecular Weight Peptides to Effect Enantioselective and Regioselective Functionalizations of Phenols

Chapter 1 discusses mechanistic studies of a peptide catalyzed desymmetrization of a class of bis(phenols). These studies eventually led to the development of a new reaction, the peptide catalyzed bromination of arenes, of which the bulk of this dissertation focuses. Chapter 2 describes the utilization of this novel reaction in the arena of asymmetric catalysis via the development of a dynamic kinetic resolution of biaryl atropisomers via this novel peptide catalyzed asymmetric bromination. Preliminary mechanistic studies towards elucidating the mechanism of this process, as well as a possible model for stereo-induction are also described. In Chapter 3 we sought to increase the utility of the enantioenriched tribrominated products through the development of a sequential regioselective cross-coupling process allowing for the synthesis of diverse atropisomerically defined highly substituted biaryl scaffolds. Chapter 4 then discusses the application of the peptide catalyzed bromination in the realm of site-selective catalysis through preliminary studies towards the peptide catalyzed site-selective bromination of the venerable glycopeptide vancomycin.