Chemistry and catalysis in supercritical media

This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The aim of this research is to explore the potential of supercritical fluids as reaction media for stoichiometric and catalytic chemical transformations in an effort to develop new, environmentally-friendly methods for chemical synthesis or processing. This approach offers the possibility of opening up substantially different chemical pathways, increasing selectivity while enhancing reaction rates, facilitating downstream separations and mitigating the need for hazardous solvents. The authors describe investigations into a number of catalytic processes for which carbon dioxide represents a viable solvent replacement. In several cases they have observed significant enhancements in selectivity and/or reactivity relative to conventional organic solvents. They have investigated the following catalytic processes: (a) selective oxidation including dihydroxylation and epoxidation, (b) asymmetric hydrogenation and hydrogen transfer reduction, (c) Lewis acid catalyzed acylation and alkylation, and (c) coupling of amines with carbon dioxide to make isocyanates