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

doi:10.1002/slct.201600875

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^*

^*Corresponding author for this work

School of Advanced Science and Engineering

Research output: Contribution to journal › Article › peer-review

12 Citations (Scopus)

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 language	English
Pages (from-to)	5141-5151
Number of pages	11
Journal	ChemistrySelect
Volume	1
Issue number	16
DOIs	https://doi.org/10.1002/slct.201600875
Publication status	Published - 2016 Oct 1

Keywords

D-fructose
boronate
boronic acid
kinetics
reaction mechanisms

ASJC Scopus subject areas

Chemistry(all)

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10.1002/slct.201600875

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

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.",

keywords = "D-fructose, boronate, boronic acid, kinetics, reaction mechanisms",

author = "Yota Suzuki and Mika Shimizu and Takuya Okamoto and Tomoaki Sugaya and Satoshi Iwatsuki and Masahiko Inamo and Takagi, {Hideo D.} and Akira Odani and Koji Ishihara",

note = "Funding Information: The authors thank Mr. Yutaro Sato and Ms. Asumi Tanaka for conducting preliminary experiments for this study. We wish to express our gratitude for financial support to JSPS KAKENHI Grant Number 25410150, and Waseda University Grant for Special Research Projects (Grant 2007B-119, 2009B-123, 2012B-153, and 2014 K-6156). We would like to thank Editage (www.edita-ge.jp) for English language editing. Publisher Copyright: {\textcopyright} 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

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doi = "10.1002/slct.201600875",

language = "English",

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T1 - Detailed Mechanism of the Reaction of Phenylboronic Acid Derivatives with D-Fructose in Aqueous Solution

T2 - A Comprehensive Kinetic Study

AU - Suzuki, Yota

AU - Shimizu, Mika

AU - Okamoto, Takuya

AU - Sugaya, Tomoaki

AU - Iwatsuki, Satoshi

AU - Inamo, Masahiko

AU - Takagi, Hideo D.

AU - Odani, Akira

AU - Ishihara, Koji

N1 - Funding Information: The authors thank Mr. Yutaro Sato and Ms. Asumi Tanaka for conducting preliminary experiments for this study. We wish to express our gratitude for financial support to JSPS KAKENHI Grant Number 25410150, and Waseda University Grant for Special Research Projects (Grant 2007B-119, 2009B-123, 2012B-153, and 2014 K-6156). We would like to thank Editage (www.edita-ge.jp) for English language editing. Publisher Copyright: © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2016/10/1

Y1 - 2016/10/1

N2 - 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.

AB - 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.

KW - D-fructose

KW - boronate

KW - boronic acid

KW - kinetics

KW - reaction mechanisms

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JO - ChemistrySelect

JF - ChemistrySelect

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ER -

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

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