2-(4-bromomethylphenyl)-1,3-dioxa-2-borinan | 162654-25-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(4-bromomethylphenyl)-1,3-dioxa-2-borinan
• 英文别名: 2-(4-(Bromomethyl)phenyl)-1,3,2-dioxaborinane；2-[4-(bromomethyl)phenyl]-1,3,2-dioxaborinane
• CAS: 162654-25-3
• 化学式: C₁₀H₁₂BBrO₂
• 分子量: 254.919
• InChiKey: XTDQDPLDIDTCCW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.71
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(10-{4-[(4-dodecyloxyphenyl)azo]phenoxy}decyl)-N,N-dimethyl amine 、 2-(4-bromomethylphenyl)-1,3-dioxa-2-borinan 以 四氢呋喃 为溶剂， 反应 48.0h， 以77%的产率得到N-[4-(dihydroxyboryl)benzyl]-N-(10-{4-[(4-dodecyloxyphenyl)azo]phenoxy}decyl)-N,N-dimethylammonium bromide
  参考文献：
  名称：

  Saccharide Induction of Chiral Orientation of the Aggregate Formed from Boronic-Acid-Appended Amphiphiles

  摘要：

  我们合成了一种硼酸双亲化合物，其链中心含有偶氮苯发色团，即 N-[4-(二羟基苄基)]-N-(10-{4-[(4-十二烷氧基苯基)偶氮]苯氧基}癸基)-N,N-二甲基溴化铵（4）。在水介质中，如果没有糖类物质，化合物 4 几乎不形成定向聚集体，但在有糖类物质存在的情况下，硼酸基团形成糖类络合物，由此产生的双亲化合物形成有序的聚集体。DSC 中的ΔH 值取决于所添加糖类的固有结构。虽然 d-葡萄糖和甲基 α-d-吡喃葡萄糖苷只能形成不太有序的聚集体，但 d-果糖和 d-木糖却能形成有序的聚集体。随着糖类固有的激子偶联带的出现，糖类与 4 的复合物变得具有 CD 活性。CD 带强度随着糖类浓度的增加而增加，但随着糖类浓度的进一步增加而降低。这些结果表明，硼酸-糖的可逆相互作用有助于诱导有序聚合体结构中的手性，其中糖被用作手性诱导的触发器。

  DOI：

  10.1246/bcsj.71.2197

文献信息

• First Successful Molecular Design of an Artificial Lewis Oligosaccharide Binding System Utilizing Positive Homotropic Allosterism
  作者：Atsushi Sugasaki、Kazunori Sugiyasu、Masato Ikeda、Masayuki Takeuchi、Seiji Shinkai

  DOI：10.1021/ja010806e

  日期：2001.10.1

  concentrations because of the sigmoidal [oligosaccharide] versus [complex] isotherm. Compound 1 has a sufficiently high affinity with Lewis oligosaccharides (K = 10(5)-10(6) M(-2)) with Hill coefficients n of 1.8-2.0, and Lewis(X) series and Lewis(a) series give opposite, symmetrical CD spectra. This is the first example of efficient binding of Lewis oligosaccharides to the artificial receptor, which has become

  我们设计了苯基硼酸基团附加的 Ce(IV) 双（卟啉）双层 1 和内消旋连接的卟啉 2，可用于生物学上重要的糖类路易斯寡糖的变构结合。由于硼酸-二醇相互作用，化合物 1 在水性介质中与路易斯寡糖结合，但由于 sigmoidal [寡糖] 与 [复杂] 等温线的关系，复合事件只能在高于临界浓度时发生。化合物1与Lewis低聚糖(K=10(5)-10(6)M(-2))具有足够高的亲和力，Hill系数n为1.8-2.0，Lewis(X)系列和Lewis(a)系列给出相反，对称的 CD 光谱。这是路易斯寡糖与人工受体有效结合的第一个例子，这已通过正同向变构成为可能。
• Mono- and oligosaccharide sensing by phenylboronic acid-appended 5,15-bis(diarylethynyl)porphyrin complexes
  作者：Osamu Hirata、Yohei Kubo、Masayuki Takeuchi、Seiji Shinkai

  DOI：10.1016/j.tet.2004.08.061

  日期：2004.11

  Porphyrin derivatives bearing a pair of boronic acid groups (1, 1 (.) Zn, and 1 Cu) were designed and synthesized from 2 to construct a saccharide sensing system. Compounds 1, 1 (.) Zn, and 1 (.) Cu have a diethynyl porphyrin rotational axis, which is expected to act as a saccharide-binding modulator. Saccharide binding studies were conducted by UV-vis, fluorescence, and circular dichroism (CD) spectroscopies. In a water-methanol 1: 1 (v/v) mixed solvent, we have found that 1 (.) Zn can bind mono- and oligosaccharides including Lewis oligosaccharides to produce 1:1 host-saccharide complexes with the association constants of 10(2) - 10(3) M-1 range. This paper thus demonstrates a new principle to design a boronic acid-based saccharide receptor. (C) 2004 Elsevier Ltd. All rights reserved.
• The First Example of Positive Allosterism in an Aqueous Saccharide-Binding System Designed on a Ce(IV) Bis(porphyrinate) Double Decker Scaffold
  作者：Atsushi Sugasaki、Masato Ikeda、Masayuki Takeuchi、Kazuya Koumoto、Seiji Shinkai

  DOI：10.1016/s0040-4020(00)00395-1

  日期：2000.6

  The first example of a positive, homotropic system in aqueous saccharide-binding has been achieved using a Ce(IV) bis(porphyrinate) double decker scaffold bearing two pairs of boronic acid groups (compound 2). In this system, the binding of the first guest (1:2 saccharide/boronic acid complex) suppresses the rotational freedom of the two porphyrin planes, which facilitates the binding of the second guest. As a result, two pairs of boronic acid groups in 2 can autoacceleratively bind these guests and yield CD-active species. The analyses of CD intensity-guest concentration plots according to the Hill equation resulted in K=3.7x10(4) M-2 and n=2.0 for D-fructose and K=9.6x10(5) M-2 and n=1.6 for D-glucose. The present system which is in action even in aqueous media is widely applicable to allosteric control of drug release, catalytic reaction, information transduction, etc. of saccharide-containing guest molecules. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Saccharide Induction of Chiral Orientation of the Aggregate Formed from Boronic-Acid-Appended Amphiphiles
  作者：Taro Kimura、Masayuki Takeuchi、Seiji Shinkai

  DOI：10.1246/bcsj.71.2197

  日期：1998.9

  A boronic-acid-appended amphiphile bearing an azobenzene chromophore at the chain center, N-[4-(dihydroxyboryl)benzyl]-N-(10-4-[(4-dodecyloxyphenyl)azo)]phenoxy}decyl)-N,N-dimethylammonium bromide (4) was synthesized. In aqueous media, compound 4 formed a scarcely-oriented aggregate in the absence of saccharides, but in the presence of saccharides the boronic acid groups formed saccharide complexes and the resultant amphiphiles formed well-ordered aggregates. The ΔH value in DSC depended on the inherent structure of the added saccharides. Although d-glucose and methyl α-d-glucopyranoside could only form less ordered aggregates, d-fructose and d-xylose formed well-ordered aggregates. The saccharide complexes with 4 became CD-active with the appearance of exciton-coupling bands inherent to the saccharides. The CD band intensity was increased with increasing saccharide concentration but decreased by a further increase in the saccharide concentration. These results indicate that the reversible boronic acid–saccharide interaction is useful to induce the chirality in the ordered aggregate structure, where saccharides are used as a trigger for the chiral induction.

  我们合成了一种硼酸双亲化合物，其链中心含有偶氮苯发色团，即 N-[4-(二羟基苄基)]-N-(10-4-[(4-十二烷氧基苯基)偶氮]苯氧基}癸基)-N,N-二甲基溴化铵（4）。在水介质中，如果没有糖类物质，化合物 4 几乎不形成定向聚集体，但在有糖类物质存在的情况下，硼酸基团形成糖类络合物，由此产生的双亲化合物形成有序的聚集体。DSC 中的ΔH 值取决于所添加糖类的固有结构。虽然 d-葡萄糖和甲基 α-d-吡喃葡萄糖苷只能形成不太有序的聚集体，但 d-果糖和 d-木糖却能形成有序的聚集体。随着糖类固有的激子偶联带的出现，糖类与 4 的复合物变得具有 CD 活性。CD 带强度随着糖类浓度的增加而增加，但随着糖类浓度的进一步增加而降低。这些结果表明，硼酸-糖的可逆相互作用有助于诱导有序聚合体结构中的手性，其中糖被用作手性诱导的触发器。