Understanding “On-Water” Catalysis of Organic Reactions. Effects of H⁺ and Li⁺ Ions in the Aqueous Phase and Nonreacting Competitor H-Bond Acceptors in the Organic Phase: On H₂O versus on D₂O for Huisgen Cycloadditions

Abstract

For a typical Huisgen cycloaddition, carried out on water, the behavior of water molecules at the oil-water interface depended on the properties of the reactants. With weakly basic reactants, a small quantity of added H(+) (HClO4, 0.0001-0.01 M) present in the aqueous phase had negligible effects, but larger quantities of H(+) (HClO4, 0.1-3.0 M) increased the catalytic effect and caused protons to cross the water-organic interface and affect the products. Added Li(+) ions (LiClO4, 0.1-3.0 M) had no effect for on-water reactions but enhanced the rates and endo products for in-water reactions. For these cycloaddition reactions, the product endo:exo ratios, when compared to those in organic solvents, can be used to distinguish between the on-water and in-water modes. Comparisons of organic reactions on H2O and on D2O indicate that on-water catalysis ranges from weak to strong trans-phase H-bonding for reactants with basic pK(a) < ca. -6 and to interfacial proton transfer for reactants with higher basic pK(a) > ca. 2 (pKa of conjugate acid). Water shows a chameleon-type response to organic molecules at hydrophobic surfaces.