Expanding the Scope of Coupling Partners in Catalytic Cross-Coupling Reactions

Title: Expanding the Scope of Coupling Partners in Catalytic Cross-Coupling Reactions
Authors: Hua, Xi Ye
Date: 2016
Abstract: Carbon-carbon (C-C) bond formation is among the most important processes in organic chemistry. Transition metal catalyzed C-C bond formation is an active research area that shows great potential due to high selectivity and relatively mild conditions. In Chapter 1, a new reaction for direct acylation of aryl halides is discussed. Specifically, the catalytic reaction between aryl halides/pseudohalides and aldehydes is explored. The choice of ligand, base, solvent, temperature, catalyst and substrates are important factors for optimizing this catalytic reaction. The various combinations of all these factors have, therefore, been examined by high-throughput screening (HTS) in order to develop the new C-C coupling reaction. In Chapter 2, a new methodology is reported in order to expand the scope of the Kumada-Corriu cross-coupling reaction. The strategy to achieve this goal is mechanistically based, matching oxidative addition rates with the rate of syringe pump addition of the Grignard to minimize the exposure of sensitive groups to the aggressive nucleophile. Aryl chlorides containing esters, amides, nitriles, pyrazines, carbamates, ketones, and other sensitive functionalities are all demonstrated to undergo chemoselective cross-coupling with this technique. The mechanistic reason for the effectiveness of this strategy is uncovered by continuous-infusion ESI-MS studies.
URL: http://hdl.handle.net/10393/35521
CollectionThèses, 2011 - // Theses, 2011 -