AEI: The "On Water" effect: Scope and mechanistic studies

ORGN 140

Sridhar Narayan, sridharn@scripps.edu, Valery V. Fokin, fokin@scripps.edu, and K. Barry Sharpless, sharples@scripps.edu. Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Rd., La Jolla, CA 92037
We recently reported that a wide variety of inter- and intramolecular reactions of hydrophobic compounds are dramatically accelerated when carried out in aqueous suspension (‘on water') relative to organic solvents or neat conditions. Several key observations, including the requirement of heterogeneity for large rate acceleration, point to the crucial role of the water-organic interface in this phenomenon. The scope of the ‘on water' effect as it applies to various pericyclic and non-pericyclic reactions will be discussed. Preliminary results from studies aimed at delineating the underlying mechanisms involved will also be presented. These include data from rate measurements and high-level computation.