In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Ross A. Widenhoefer of the Department of Chemistry at Duke University will explore the synthesis and study of potential intermediates in gold(I) pi-activation catalysis, including pi-alkene, pi-allene, and sigma-vinyl complexes. An understanding of the mechanisms of gold pi-activation catalysis has lagged significantly behind the synthetic development of this chemistry, and available information is largely derived from computational analyses. As such, little experimental information is available regarding the behavior of gold pi- and sigma-complexes generated as intermediates in gold(I)-catalyzed hydrofunctionalization and likewise, experimental information regarding the structure and reactivity of cationic gold carbene complexes germane to gold-catalyzed alkene cyclopropanation and enyne cycloaddition is lacking. The proposed research activities aim to fill these gaps and to develop an experimentally-grounded understanding of the mechanisms of gold pi-activation catalysis.
The emergence of cationic gold(I) complexes as catalysts for the functionalization of carbon carbon multiple bonds (pi-activation catalysis) represents one of the most important developments in homogenous catalysis over the past decade. These transformations often display high efficiency, excellent atom economy, and high regio- and stereoselectivity, making them particularly attractive for application in both target-oriented synthesis and pharmaceutical development. The research activities undertaken in this project will provide mechanistic information that will facilitate the continued development of this important family of synthetic transformations. In addition, the research activities related to this project are fully integrated with the scientific education and training of the graduate and undergraduate research participants including students from ethnic groups traditionally underrepresented in the sciences.
