Detailed Mechanism of the Reaction of Phenylboronic Acid Derivatives with D-Fructose in Aqueous Solution: A Comprehensive Kinetic Study

Yota Suzuki, Mika Shimizu, Takuya Okamoto, Tomoaki Sugaya, Satoshi Iwatsuki, Masahiko Inamo, Hideo D. Takagi, Akira Odani, Koji Ishihara

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    Abstract

    A detailed kinetic study of the reactions of phenylboronic acid (PhB(OH)2), 2-methylphenylboronic acid (2-MePhB(OH)2), 2-isopropylphenylboronic acid (2-iPrPhB(OH)2), and 1-hydroxy-3H-2,1-benzoxaborole (BxB(OH)) with D-fructose was carried out to clarify the nature of the reactive boron species in D-fructose sensing and investigate the corresponding reaction mechanism. Both the boronic acids (RB(OH)2) and boronate ions (RB(OH)3 ) were reactive toward D-fructose, while out of the five D-fructose anomers only α-D-fructofuranose was reactive toward boron species. The reactions of all substrates proceeded consecutively in two steps (steps 1 and 2). We concluded that the first intermolecular step (step 1) corresponds to the parallel reactions (two parallel reactions for 2-iPrPhB(OH)2 and three for the other systems) of the boronic acid and the boronate ion with α-D-fructofuranose to form bicoordinate complexes (mixture of exo- and endo-isomers), and the second intramolecular step (step 2) corresponds to the formation of a tricoordinate α-D-fructofuranose complex from the bicoordinate complexes. It was found that both the boronic acid and the boronate ion were kinetically reactive toward D-fructose, with the latter being more reactive.

    Original languageEnglish
    Pages (from-to)5141-5151
    Number of pages11
    JournalChemistrySelect
    Volume1
    Issue number16
    DOIs
    Publication statusPublished - 2016 Jan 1

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    Keywords

    • boronate
    • boronic acid
    • D-fructose
    • kinetics
    • reaction mechanisms

    ASJC Scopus subject areas

    • Chemistry(all)

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