Universal Reaction Mechanism of Boronic Acids with Diols in Aqueous Solution: Kinetics and the Basic Concept of a Conditional Formation Constant.

To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants ( ${K{{{\rm BL}\hfill \atop {\rm a}\hfill}}}$) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The p Ka values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined p Ka values of HBLs. The use of the conditional formation constant, K′, based on the main reaction: RB(OH)2+H2L ${{\mathop \leftrightarrow \limits ^{K{_{1}}}_{}}}$ RB(L)(OH)−+H3O+ instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B′) with uncomplexed diol species (L′) to form boronic acid diol complex species (esters, BL′) in aqueous solution at pH 5-11: B′+L′ ${{\mathop \leftrightarrow \limits ^{K{^\prime}}_{}}}$ BL′. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. [ABSTRACT FROM AUTHOR]