Micellar Mechanisms for Desymmetrization Reactions in Aqueous Media.

Abstract

Water-mediated organic reactions significantly contribute to the protection of the environment. Desymmetrization reactions, which convert only one of the identical functional groups within one molecule, are cost-effective because of the low cost of the starting materials. In combination with these two merits, highly efficient and practical selective monohydrolysis reactions of symmetric diesters were previously reported. The products of these reactions are versatile building blocks. The mechanisms of this reaction are hypothesized to proceed through micellar aggregates in which the hydrophilic carboxylate anions formed by monohydrolysis are directed outward and the remaining hydrophobic groups are directed inward in governing the selectivities. Here, dynamic light scattering and electrophoretic light scattering experiments were performed for detection of the key intermediates in the reaction. These experiments revealed the existence of aggregates with negative charges on the surface in the mainly aqueous media, supporting the reaction mechanisms that control the high selectivities.