The Chemical Catalysis Program of the Chemistry Division supports the research of Professors Steven T. Diver and Jerome B. Keister. Professor Diver and Professor Keister are faculty members in the Department of Chemistry at the University at Buffalo, the State University of New York. Ene-yne metathesis is a metal-catalyzed reaction that brings together two molecules, one with a carbon-carbon double bond and the other with a carbon-carbon triple bond. The two molecules are linked together by the action of the catalyst. The reaction is widely used in organic synthesis and materials chemistry. The ene-yne reaction, however, is difficult to study and the selectivity is hard to predict. The goal of this project is to better understand the structure of the intermediates and the catalytic cycle. A better understanding of reactive intermediates facilitates the prediction of selectivity and the design of better catalysts. Graduate students and undergraduates are trained in organic, organometallic, and inorganic chemistry through their participation in the project. Additional outreach efforts at the elementary school level develop scientific awareness in eager young minds, and often give students their first exposure to the many roles of molecules in our world.
The Grubbs ruthenium carbenes have improved organic synthesis. Alkene metathesis and ene-yne metathesis are widely used in the synthesis of natural products, pharmaceuticals agents, and organic materials. However, decomposition of catalytic intermediates and low selectivity in cross metathesis are two fundamental problems that limit the efficiency and scope of these powerful reactions. In this collaborative project, a research team led by Drs. Diver and Keister are developing the Buchner reaction to trap reactive intermediates and thus study of mechanism of these reactions. Key questions center on the decomposition pathways and reactivity of ruthenium vinyl carbenes. The reactivity of substituted vinyl carbenes has not been evaluated previously, despite the importance of these intermediates in the ene-yne pathway. Quenching of metathesis reactions continues to be a problem and reliable, rapid methods for quenching a wide variety of ruthenium catalysts is an important goal of the project. Solid-supported isocyanides are being developed and used for the quenching and removal of ruthenium carbenes. Dr. Diver presents a molecular science course for non-majors at SUNY Buffalo that increases general scientific literacy of the University students.
