Expanding the Scope of Available Iron-Based Catalysts for Suzuki-Miyaura Cross-Coupling Reactions Through Ligand Design and Mechanistic Investigation

Abstract

This dissertation describes the design and logic that went into the development of Suzuki-Miyaura cross-coupling reactions catalyzed by iron-based complexes. Chapter 1 provides an overview into the field of iron cross-coupling and the comparison to state-of-the art nickel-based systems. A combination of methodology development and mechanistic insight will be discussed. Chapter 2 describes the initial discovery and optimization of a Suzuki-Miyaura cross-coupling reaction between alkyl halides and unactivated arylboronic pinacol esters catalyzed by an iron cyanobis(oxazoline) complex. Chapter 3 discusses the extension of the catalytic system developed in Chapter 2 to an enantioselective reaction to afford chiral 1,1-diarylalkanes. The dissertation concludes with Chapter 4 which describes the development of a C³-C³ Suzuki-Miyaura reaction catalyzed by a β-diketiminate iron complex. Ligand design and mechanistic studies are discussed here to provide insight into the mechanistic intricacies of the reaction and its effect on future reaction development.