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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

Organic chemistry

Recommended Citation

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

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