Inorganic Chemistry Commons^™

Nickel-Catalyzed Oxidative Decarboxylative (Hetero)Arylation Reactions, Aaron P. Honeycutt

Graduate Theses, Dissertations, and Problem Reports

Transition-metal-catalyzed decarboxylative coupling reactions have gained considerable attention over the past decade as an efficient route to form heterobiaryls. However, current methods for oxidative decarboxylative (hetero)arylation with unactivated C-H bonds have been limited by poor substrate scope, control of regioselectivity, and chemospecificity. This thesis describes the development of a new nickel-catalyzed oxidative decarboxylative coupling (ODC) with unactivated C-H bonds. The first chapter discusses the development of the new nickel-catalyzed ODC reaction to enable the coupling of a N,N'-bidentate directing group with a broad scope of heteroaromatic carboxylates and ortho-substituted benzoates, a scope that has not been achieved in previous …

Oxidative C-C Bond Formation Reactivity Of High Valent Nickel And Palladium Complexes, Michael Benjamin Watson

Arts & Sciences Electronic Theses and Dissertations

The development of both palladium and nickel catalysis over the past several decades has led to the ability to perform a multitude of C-C coupling, C-Heteroatom coupling, and C-H functionalization reactions. These reactions typically utilize a catalytic cycle involving Pd0/II/IV and Ni0/II. While using these types of catalytic cycles one can create a multitude of different hard to make bonds, it is always important to keep expanding what we view as potential catalytic intermediates to keep developing new cycles capable of new transformations. One such way to expand our knowledge of these catalytic cycles is to look at the oxidation …

High-Valent Organometallic Palladium And Nickel Complexes And Their Roles In Carbon-Carbon And Carbon-Heteroatom Bond Formation Reactions, Jason Wesley Schultz

Arts & Sciences Electronic Theses and Dissertations

The development of palladium catalysis has been influential in a wide range of organic transformations, in particular C-C coupling, C-Heteroatom coupling and C-H functionalization reactions. These catalytic transformations normally proceed through the Pd0/II catalytic cycle. These reactions are remarkably useful, however, they suffer from two major problems: -hydride elimination and palladium black deposition. To circumvent these problems, recent reports have been focused on developing novel organic transformations proceeding through high-valent palladium and nickel catalytic cycles.

To this point, we recently reported the isolation and characterization of various mononuclear PdIII complexes using the tetradentate ligands, N,N-di-alkyl-2,11-diaza[3.3](2,6)pyridinophane (RN4, R = tBu, iPr, …