17-Phenoxy-3,31-diphenyl-16,18-dioxa-17-boraheptacyclo[17.12.0.02,15.05,14.08,13.020,29.021,26]hentriaconta-1(31),2,4,6,8,10,12,14,19,21,23,25,27,29-tetradecaene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 17-Phenoxy-3,31-diphenyl-16,18-dioxa-17-boraheptacyclo[17.12.0.02,15.05,14.08,13.020,29.021,26]hentriaconta-1(31),2,4,6,8,10,12,14,19,21,23,25,27,29-tetradecaene
• 化学式: C₄₆H₂₉BO₃
• 分子量: 640.545
• InChiKey: RJUYTFIQIZQDAE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.14
• 重原子数：
  50
• 可旋转键数：
  4
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  三苯基硼酸酯 、 (R)-2,2'-二苯基-3,3'-(4-联菲酚) 以 四氯化碳 为溶剂， 反应 1.0h， 生成 17-Phenoxy-3,31-diphenyl-16,18-dioxa-17-boraheptacyclo[17.12.0.02,15.05,14.08,13.020,29.021,26]hentriaconta-1(31),2,4,6,8,10,12,14,19,21,23,25,27,29-tetradecaene
  参考文献：
  名称：

  衍生自VANOL和VAPOL配体的硼酸盐催化剂的催化不对称叠氮化：范围和机理研究。

  摘要：

  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

  DOI：

  10.1002/chem.200701558

文献信息

• <i>BOROX Catalysis:</i> Self-assembled <scp>amino</scp>-BOROX and <scp>imino</scp>-BOROX Chiral Brønsted Acids in a Five Component Catalyst Assembly/Catalytic Asymmetric Aziridination
  作者：Anil K. Gupta、Munmun Mukherjee、Gang Hu、William D. Wulff

  DOI：10.1021/jo301064u

  日期：2012.9.21

  was observed since, while 10 different products could have resulted from various reactions between the five components, an aziridine was formed in 85% yield and 98% ee and only two other products could be detected in 3% yield. Studies reveal that the first in a sequence of three reactions is an exceedingly rapid amine-induced assembly of an amino-BOROX chiral Brønsted acid species from VAPOL and B(OPh)3

  描述了从醛、胺、重氮乙酸乙酯、B(OPh) 3和拱形联芳基配体(VAPOL或VANOL)分子开始的五组分催化剂组装/氮丙啶化反应。观察到显着水平的化学选择性，因为虽然五种成分之间的各种反应可能产生 10 种不同的产物，但氮丙啶以 85% 的产率和 98% 的 ee 形成，而仅检测到另外两种产物，产率为 3% . 研究表明，三个反应序列中的第一个是来自 VAPOL 和 B(OPh) 3的氨基-BOROX 手性布朗斯台德酸物质的极其快速的胺诱导组装，然后由胺和醛形成亚胺，然后伴随形成亚氨基-BOROX 手性布朗斯台德酸，最后亚胺与重氮乙酸乙酯在亚氨基-BOROX 催化剂的介导下反应，得到具有非常高的非对映选择性和对映选择性的氮丙啶-2-羧酸酯。
• 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。
• Substrate-Induced Covalent Assembly of a Chemzyme and Crystallographic Characterization of a Chemzyme−Substrate Complex
  作者：Gang Hu、Anil K. Gupta、Rui H. Huang、Munmun Mukherjee、William D. Wulff

  DOI：10.1021/ja1070224

  日期：2010.10.20

  A substrate induced covalent assembly of a highly organized chemzyme known to be effective in both catalytic asymmetric aziridination and aza Diels-Alder reactions is described and the information gained from which led to an efficient one-pot aziridination protocol. The crystal structures of two chemzyme-iminium complexes were elucidated by X-ray diffraction analysis that provides critical insights into the binding of the substrates with the chemzyme.
• Evidence for a Boroxinate Based Brønsted Acid Derivative of VAPOL as the Active Catalyst in the Catalytic Asymmetric Aziridination Reaction
  作者：Gang Hu、Li Huang、Rui H. Huang、William D. Wulff

  DOI：10.1021/ja904589k

  日期：2009.11.4

  Studies are described that were designed to determine the structure of the active catalyst in the asymmetric catalytic aziridination of imines with ethyl diazoacetate (AZ reaction). Evidence suggests that the active catalyst contains a boroxine ring in which one of the three boron atoms is spiro-fused with the two phenol groups of the VAPOL tigand. B-11 and H-1 NMR evidence supports the boroxinate structure B in which the counterion to the boroxinate is the protonated form of the imine. The boroxinate structure is also supported by two solid state structures of a VAPOL boroxinate in which the gegen cation is tetramethyl ammonium and 4-dimethylaminopyridinium.
• 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