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Methodology and mechanism: Reinvestigating the Ullmann reaction

Derek Van Allen, University of Massachusetts - Amherst

Abstract

We have combined the tools of organometallic chemistry with those of organic chemistry, and explored methodology and mechanism of palladium and copper-based catalysis. Organometallic chemistry plays a prominent role in industrial and academic laboratories, and developments in this field continue to expand our fundamental understating of chemical reactions. Herein, we report on a specific failure of a palladium-catalyzed coupling reaction, and the subsequent development of alternative copper-based methodologies. We have developed a new cross coupling protocol for the synthesis of unsymmetrical triarylphosphines, using copper-based catalysis. Furthermore, we conducted a thorough investigation into the mechanism of the centuryold Ullmann coupling. Our mechanistic research is based on rational experimental design intended to address fundamental questions regarding copper-based catalysis. One such question is: what is the nature of the reaction intermediate( s); our data is inconsistent with copper(III) intermediates. ^

Subject Area

Chemistry, Organic

Recommended Citation

Derek Van Allen, "Methodology and mechanism: Reinvestigating the Ullmann reaction" (January 1, 2004). Doctoral Dissertations Available from Proquest. Paper AAI3136788.
http://scholarworks.umass.edu/dissertations/AAI3136788

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