Detailed Mechanism of the Reaction of Phenylboronic Acid Derivatives with D‐Fructose in Aqueous Solution: A Comprehensive Kinetic Study
Detailed Mechanism of the Reaction of Phenylboronic Acid Derivatives with D‐Fructose in Aqueous Solution: A Comprehensive Kinetic Study
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苯基硼酸衍生物与 D-果糖在水溶液中反应的详细机制：综合动力学研究
DOI：
10.1002/slct.201600875
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
K. Ishihara
中科院分区：
文献类型：
--
作者：
Yota Suzuki;M. Shimizu;T. Okamoto;Tomoaki Sugaya;S. Iwatsuki;M. Inamo;H. Takagi;A. Odani;K. Ishihara
对苯基硼酸（PhB（OH）2）、2-甲基苯基硼酸（2-MePhB（OH）2）、2-异丙基苯基硼酸（2-iPrPhB（OH）2）和1-羟基-3H-2，1-苯并氧杂硼杂环戊烯（BxB（OH））与D-果糖的反应进行了详细的动力学研究，以阐明D-果糖传感中反应性硼物种的性质并研究相应的反应机理。硼酸（RB（OH）2）和硼酸根离子（RB（OH）3−）都对D-果糖有反应性，而在五种D-果糖端基异构体中，只有α-D-呋喃果糖对硼物种有反应性。所有底物的反应在两个步骤（步骤1和2）中连续进行。我们得出结论，第一个分子间步骤（步骤1）对应于平行反应硼酸和硼酸根离子与α-D-呋喃果糖形成双配位络合物（2-iPrPhB（OH）2为两个平行反应，其它体系为三个平行反应）（外-和内-异构体的混合物），第二个分子内步骤（步骤2）对应于从双配位复合物形成三配位α-D-呋喃果糖复合物。结果发现，硼酸和硼酸根离子都对D-果糖具有动力学反应性，后者更具反应性。
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.
影响因子：
4.6
作者：
Iwatsuki, Satoshi;Nakajima, Shihoko;Ishihara, Koji
通讯作者：
Ishihara, Koji
3-硝基苯基硼酸在与乙二醇和丙二醇反应中与其共轭硼酸离子相比具有高反应性的动力学证据
DOI：
--
发表时间：
2008
期刊：
Inorganic Chemistry 47
影响因子：
--
作者：
Eiko Nakano;Satoshi Iwatsuki;Masahiko Inamo;Hideo D. Takagi;and Koji Ishihara;Eiko Nakano;Chiaki Miyamoto
通讯作者：
Chiaki Miyamoto