Fundamental Study on the Reactivity of 4-Pyridylboronic Acid Derivatives with Strong Acidities

Satoshi Iwatsuki, Hidetaka Ohara, Yuki Kanamitsu, Koji Ishihara

    Research output: Contribution to journalArticle

    3 Citations (Scopus)

    Abstract

    The acid dissociation constants (Ka) of 4-pyridylboronic acid derivatives were determined spectrophotometrically, and the pKaassignment was performed based on 11B NMR spectroscopy. It was found that both of the boron centers in 4-pyridylboronic acid (4-PyB(OH2) and the N-methylated derivative [4-(N-Me)Py+B(OH)2] have strong acidities (pKaB= 4.00 and 3.96, respectively), indicating that the introduction of a methyl group into the nitrogen atom of the pyridine ring in 4-pyridylboronic acid has no influence on the acidity of the boron center. Kinetic studies on the complexation reactions of 4-(N-X)Py+B(OH)2(X = H, Me) with hinokitiol (Hipt) were carried out under pseudo first-order conditions, where the total concentration of boronic acid was much larger than that of Hipt. Both 4-HPy+B(OH)2and 4-(N-Me)Py+B(OH)2reacted with Hipt much faster than their conjugate boronate ions (4-HPy+B(OH)3-and 4-(N-X)Py+B(OH)3-, respectively), which is consistent with our recent results. The rate constants (k1) for the reactions of the boronic acids with Hipt increase with an increase of the acidity of boronic acid. The reactivity of 4-(N-Me)Py+B(OH)2, having the strongest acidity (pKaB= 3.96), was still higher than the phenyl and pyridyl boronic acid derivatives having pKaB= /4.40 - 10.74, which we have examined so far.

    Original languageEnglish
    Pages (from-to)1041-1047
    Number of pages7
    JournalBunseki Kagaku
    Volume61
    Issue number12
    DOIs
    Publication statusPublished - 2012

    Fingerprint

    Boronic Acids
    Acidity
    Derivatives
    Acids
    Boron
    Complexation
    Nuclear magnetic resonance spectroscopy
    Rate constants
    Nitrogen
    Ions
    Atoms
    Kinetics

    Keywords

    • acid dissociation
    • pyridylboronic acid
    • reaction kinetics
    • reactivity

    ASJC Scopus subject areas

    • Analytical Chemistry

    Cite this

    Fundamental Study on the Reactivity of 4-Pyridylboronic Acid Derivatives with Strong Acidities. / Iwatsuki, Satoshi; Ohara, Hidetaka; Kanamitsu, Yuki; Ishihara, Koji.

    In: Bunseki Kagaku, Vol. 61, No. 12, 2012, p. 1041-1047.

    Research output: Contribution to journalArticle

    Iwatsuki, Satoshi ; Ohara, Hidetaka ; Kanamitsu, Yuki ; Ishihara, Koji. / Fundamental Study on the Reactivity of 4-Pyridylboronic Acid Derivatives with Strong Acidities. In: Bunseki Kagaku. 2012 ; Vol. 61, No. 12. pp. 1041-1047.
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    N2 - The acid dissociation constants (Ka) of 4-pyridylboronic acid derivatives were determined spectrophotometrically, and the pKaassignment was performed based on 11B NMR spectroscopy. It was found that both of the boron centers in 4-pyridylboronic acid (4-PyB(OH2) and the N-methylated derivative [4-(N-Me)Py+B(OH)2] have strong acidities (pKaB= 4.00 and 3.96, respectively), indicating that the introduction of a methyl group into the nitrogen atom of the pyridine ring in 4-pyridylboronic acid has no influence on the acidity of the boron center. Kinetic studies on the complexation reactions of 4-(N-X)Py+B(OH)2(X = H, Me) with hinokitiol (Hipt) were carried out under pseudo first-order conditions, where the total concentration of boronic acid was much larger than that of Hipt. Both 4-HPy+B(OH)2and 4-(N-Me)Py+B(OH)2reacted with Hipt much faster than their conjugate boronate ions (4-HPy+B(OH)3-and 4-(N-X)Py+B(OH)3-, respectively), which is consistent with our recent results. The rate constants (k1) for the reactions of the boronic acids with Hipt increase with an increase of the acidity of boronic acid. The reactivity of 4-(N-Me)Py+B(OH)2, having the strongest acidity (pKaB= 3.96), was still higher than the phenyl and pyridyl boronic acid derivatives having pKaB= /4.40 - 10.74, which we have examined so far.

    AB - The acid dissociation constants (Ka) of 4-pyridylboronic acid derivatives were determined spectrophotometrically, and the pKaassignment was performed based on 11B NMR spectroscopy. It was found that both of the boron centers in 4-pyridylboronic acid (4-PyB(OH2) and the N-methylated derivative [4-(N-Me)Py+B(OH)2] have strong acidities (pKaB= 4.00 and 3.96, respectively), indicating that the introduction of a methyl group into the nitrogen atom of the pyridine ring in 4-pyridylboronic acid has no influence on the acidity of the boron center. Kinetic studies on the complexation reactions of 4-(N-X)Py+B(OH)2(X = H, Me) with hinokitiol (Hipt) were carried out under pseudo first-order conditions, where the total concentration of boronic acid was much larger than that of Hipt. Both 4-HPy+B(OH)2and 4-(N-Me)Py+B(OH)2reacted with Hipt much faster than their conjugate boronate ions (4-HPy+B(OH)3-and 4-(N-X)Py+B(OH)3-, respectively), which is consistent with our recent results. The rate constants (k1) for the reactions of the boronic acids with Hipt increase with an increase of the acidity of boronic acid. The reactivity of 4-(N-Me)Py+B(OH)2, having the strongest acidity (pKaB= 3.96), was still higher than the phenyl and pyridyl boronic acid derivatives having pKaB= /4.40 - 10.74, which we have examined so far.

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