三(对甲基苯基)硼酸盐 | 14643-62-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 三(对甲基苯基)硼酸盐
• 英文名称: tris(p-methylphenyl) borate
• 英文别名: Tri-p-tolyl borate；tris(4-methylphenyl) borate
• CAS: 14643-62-0
• 化学式: C₂₁H₂₁BO₃
• 分子量: 332.207
• InChiKey: ROEKPHSQKWBJKS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.13
• 重原子数：
  25.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  三(对甲基苯基)硼酸盐 在 甲胺 作用下， 以100%的产率得到
  参考文献：
  名称：

  Elter, G.; Glemser, O.; Herzog, W., Chemische Berichte, 1972, vol. 105, p. 115 - 124

  摘要：

  DOI：
• 作为产物：
  描述：

  对甲酚 在 dimethyl sulfide borane 作用下， 以 四氢呋喃 为溶剂， 生成 三(对甲基苯基)硼酸盐
  参考文献：
  名称：

  苯酚衍生物与芳基氮丙啶的位置和立体选择性碳-碳偶联反应。

  摘要：

  易于获得的芳基硼酸酯与N保护的芳基氮丙啶的化学，区域和立体选择性直接碳-碳偶联提供了一种合成新的2-（o-羟基芳基）-2-芳基乙胺的方法，以新颖的环化顺序，得到立体定义的取代的3-芳基二氢吲哚。[反应：看文字]

  DOI：

  10.1021/ol060822m

文献信息

• Synthesis of Highly Enantioenriched Propelladienes and their Application as Ligands in Asymmetric Rh-Catalyzed 1,4-Additions
  作者：Tommaso Pecchioli、Mathias Christmann

  DOI：10.1021/acs.orglett.8b02204

  日期：2018.9.7

  The first synthesis of highly enantioenriched [4.3.3]propelladienes is reported. The novel bridged bicyclo[3.3.0] dienes were applied as steering ligands in the rhodium-catalyzed asymmetric arylation of cyclic enones. The catalytic system showed high catalytic activity, and the 1,4-adducts were obtained in good to excellent yields (46–99%) with enantioselectivities up to 96% ee.

  据报道，首次合成了高度对映体富集的[4.3.3]丙二烯。新型桥联双环[3.3.0]二烯用作铑催化的环状烯酮的不对称芳基化反应的配位体。催化体系显示出较高的催化活性，并且1,4-加合物以良好至优异的收率（46–99％）获得，对映选择性高达ee的96％。
• Catalytic Asymmetric Aziridination with Borate Catalysts Derived from VANOL and VAPOL Ligands: Scope and Mechanistic Studies
  作者：Yu Zhang、Aman Desai、Zhenjie Lu、Gang Hu、Zhensheng Ding、William D. Wulff

  DOI：10.1002/chem.200701558

  日期：2008.4.18

  An extended study of the scope and mechanism of the catalytic asymmetric aziridination of imines with ethyl diazoacetate mediated by catalysts prepared from the VANOL and VAPOL ligands and triphenylborate is described. Nonlinear studies with scalemic VANOL and VAPOL reveal an essentially linear relationship between the optical purity of the ligand and the product suggesting that the catalyst incorporates

  描述了由VANOL和VAPOL配体以及硼酸三苯酯制备的催化剂介导的亚胺与重氮乙酸乙酯催化不对称叠氮化的范围和机理的扩展研究。用鳞状VANOL和VAPOL进行的非线性研究表明，配体和产物的光学纯度之间存在基本线性的关系，这表明催化剂掺入了单个配体分子。由（1）H NMR研究表明，由B（OPh）（3）制备的催化剂中存在两种物质，或者是VANOL或VAPOL。催化剂混合物的质谱分析表明，一种物质涉及一个配体分子和一个硼原子（B1），另一种物质涉及一个配体和两个硼原子（B2）。后者可以配制成线性或环状焦硼酸盐，（11）B NMR谱图与线性焦硼酸盐结构最一致。已开发出几种用于催化剂制备的新方案，其允许生成比例为10：1至1:20的B1和B2催化剂的混合物。对富含B1和B2物种的催化剂的研究表明，B2催化剂是VAPOL催化的不对称叠氮化反应中的活性催化剂，比B1催化剂具有更高的不对称诱导率和速率。差异
• A new regio- and stereoselective intermolecular Friedel–Crafts alkylation of phenolic substrates with aryl epoxides
  作者：Ferruccio Bertolini、Paolo Crotti、Franco Macchia、Mauro Pineschi

  DOI：10.1016/j.tetlet.2005.10.138

  日期：2006.1

  A conceptually new regioselective and highly syn-stereoselective intermolecular Friedel–Crafts-type O-alkylation of phenols with aryl epoxides by the use of appropriately substituted aryl borates is reported. The carbon–carbon bond formation occurs in neutral and mild conditions without the need for external Lewis acids or transition metal catalysts.

  概念上的新的区域选择性和高顺式报道通过使用适当取代的芳基硼酸盐的分子间-stereoselective的Friedel-Crafts型芳基的环氧化物酚的O-烷基化。碳-碳键的形成发生在中性和温和条件下，不需要外部路易斯酸或过渡金属催化剂。
• Copper-catalyzed electrophilic amination using N-methoxyamines
  作者：Yutaro Fukami、Takamasa Wada、Tatsuhiko Meguro、Noritaka Chida、Takaaki Sato

  DOI：10.1039/c5ob02167g

  日期：——

  Copper-catalyzed electrophilic amination using functionalizedN-methoxyamines, prepared by nucleophilic addition toN-methoxyamides, is reported.

  使用功能化的N-甲氧胺进行铜催化的电亲合胺化反应，该N-甲氧胺是通过亲核加成到N-甲氧酰胺制备的。
• The Nature of meso- and pyro-Borate Precatalysts to the VANOL and VAPOL BOROX Catalysts
  作者：Wenjun Zhao、Xiaopeng Yin、Anil K. Gupta、Xin Zhang、William D. Wulff

  DOI：10.1055/s-0034-1378707

  日期：2015.7

  The structures of the meso- and pyro-borate esters generated by treatment of the VANOL and VAPOL ligands with triphenylborate have been revisited. These species were previously identified as precatalysts that could be in situ converted into VANOL and VAPOL BOROX catalysts by an imine substrate. The complete assignment of all protons for both the meso- and pyro-borate esters of both ligands was aided by the 1H NMR spectrum of each generated from pentadeuterophenol. There were significant differences between the chemical shifts for certain protons in the meso- and pyro-borate species in both the VANOL and VAPOL derivatives. Optimized structures for the meso-borates and two different isomers of the pyro-borates were determined by DFT calculations for each ligand. For each ligand the cyclic pyro-borate was found to be lower in energy than the corresponding linear pyro-borate at the B3LYP/6-311+G(d,p) level of theory. The structures of the cyclic pyro-borate esters were more consistent with the observed 1H NMR chemical shifts than the linear pyro-borates for each ligand and thus the structures of the pyro-borates esters of VANOL and VAPOL have been re-assigned as the cyclic isomers.

  通过三苯基硼处理VANOL和VAPOL配体生成的中间体和热分解硼酸酯结构进行了重新研究。这些物种先前被确定为可以通过亚胺底物在原位转化为VANOL和VAPOL BOROX催化剂的前催化剂。通过从五重氘苯酚中生成的每个1H NMR光谱，为两种配体的中间体和热分解硼酸酯的所有质子进行了完整的指定。在VANOL和VAPOL衍生物的中间体和热分解硼酸酯物种中，某些质子的化学位移存在显着差异。通过DFT计算确定了每种配体的中间体和两种不同异构体的热分解硼酸酯的优化结构。对于每种配体，循环热分解硼酸酯在B3LYP/6-311+G(d,p)理论水平下的能量低于相应的线性热分解硼酸酯。对于每种配体，循环热分解硼酸酯酯的结构与观察到的1H NMR化学位移更一致，因此VANOL和VAPOL的热分解硼酸酯酯的结构已被重新指定为循环异构体。