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Title: Studies in Nickel-Catalyzed Cross Coupling: Mechanistic Investigations of Iminium Oxidative Addition and the Development of a Phosphine Framework for Nickel Catalysis
Authors: Wu, Kevin
Advisors: Doyle, Abigail G
Contributors: Chemistry Department
Keywords: Cross Coupling
Ligand Development
Nickel Catalysis
Organometallic Catalysis
Oxidative Addition
Subjects: Organic chemistry
Inorganic chemistry
Issue Date: 2017
Publisher: Princeton, NJ : Princeton University
Abstract: Transition metal-catalyzed cross coupling has developed into one of the most powerful synthetic strategies in all of chemistry. Crucial to the success of cross coupling has been its incredible versatility in terms of coupling partner scope and the development of highly active Pd catalysts which permit coupling under extremely mild conditions. In this thesis, we describe two projects in the rapidly growing field of Nicatalyzed cross coupling. First, we disclose mechanistic studies on the oxidative addition of iminium ions to nickel in the context of catalytic reactions. Iminium and oxocarbenium ions are an underexplored class of electrophiles, and their incorporation into cross coupling could yield valuable α-substituted amines and ethers. Organometallic and stereochemical studies in support of the iminium mechanism are reported, as well as examples of oxidative addition to iminium salts in catalytic contexts. Second, we detail the development and structural characterization of a modular and novel class of phosphines for enabling Ni catalysis. Our studies find that existing ligands, including those designed for Pd, are ineffective in the Ni-catalyzed Suzuki coupling of acetals, prompting us to investigate new phosphine architectures. The properties of the phosphine ligands are quantified using molecular parameters. Regression analysis identifies a correlation between remote steric hindrance and ligand effectiveness, a concept that could guide future ligand design for nickel. Our study also uncovers a disparity between cone angle and % buried volume, two steric parameters previously believed to be equivalent. We expect that research disclosed in this thesis will benefit the field of Ni-catalyzed cross coupling by both expanding the substrate scope and enhancing the activity of Ni catalysts.
Alternate format: The Mudd Manuscript Library retains one bound copy of each dissertation. Search for these copies in the library's main catalog:
Type of Material: Academic dissertations (Ph.D.)
Language: en
Appears in Collections:Chemistry

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