rac-diethylammonium tris(tetrachlorobenzenediolato)phosphate(V) | 140176-15-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: rac-diethylammonium tris(tetrachlorobenzenediolato)phosphate(V)
• 英文别名: rac-diethylammonium TRISPHAT；[Et2NH2][rac-TRISPHAT]
• CAS: 140176-15-4
• 化学式: C₄H₁₂N*C₁₈Cl₁₂O₆P
• 分子量: 842.75
• InChiKey: ISDMCBROENAVAX-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  13.55
• 重原子数：
  42.0
• 可旋转键数：
  2.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  67.41
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (-)-(R_a)-4,5-dihydro-3H-4-[(S)-3,3-dimethylbutan-2-yl]dinaphth[2,1-c;1'2'-e]azepine 、 rac-diethylammonium tris(tetrachlorobenzenediolato)phosphate(V) 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 氯仿 、 丙酮 为溶剂， 反应 0.36h， 以86%的产率得到(-)-(R_a)-[(S)-3,3-dimethybutan-2-yl]-3H-4-azepinium-cyclohepta[2,1-a;3,4-a']dinaphthalene tris(tetrachlorobenzenediolato)phosphate (V)
  参考文献：
  名称：

  Enantioselective olefin epoxidation using novel biphenyl and binaphthyl azepines and azepinium salts

  摘要：

  Homologous biphenyl and (diastereomeric) binaphthyl tertiary azepines and quaternary iminium salts were prepared from (S)- and (R)-3,3-dimethylbutan-2-amine. Both the amines and iminium ions behave as effective catalysts for the enantioselective epoxidation of unfunctionalized olefins (ee up to 87%). (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.08.018
• 作为产物：
  描述：

  四氯邻苯二酚 、 二乙胺 在 五氯化磷 作用下， 以 甲苯 、 二氯甲烷 为溶剂， 反应 26.0h， 以86%的产率得到rac-diethylammonium tris(tetrachlorobenzenediolato)phosphate(V)
  参考文献：
  名称：

  使用Tropos二苯并ze庚因催化剂的双相对映选择性烯烃环氧化

  摘要：

  已制备了几种新颖的手性亚胺鎓TRISPHAT [三（四氯代苯并二氨基苯基）磷酸盐（V）]盐，该盐结合了二苯基a庚啶核，手性外环附件和亲脂性抗衡离子，并在双相对映选择性烯烃环氧化条件下进行了测试。有趣的是，衍生自可商购获得的（S）-或（R）-1,2,2-三甲基丙胺的亚胺盐可以显示出与由1-丙酮胺制成的那些相似的效率。进行可变温度NMR光谱（VT-NMR）和圆二色性（CD）实验，以寻找产物中良好的对映选择性与催化剂的联苯轴向手性的高非对映异构体控制之间的相关性。

  DOI：

  10.1021/jo050629q

文献信息

• Towards the stereoselective synthesis of inherently chiral pseudorotaxanes
  作者：Pierre Mobian、Natalie Banerji、Gérald Bernardinelli、Jérôme Lacour

  DOI：10.1039/b513562a

  日期：——

  determination of the association constants (Ka) was afforded. The crucial role played by the ammonium counter-ion in the threading process was further demonstrated as salts of TRISPHAT (tris(tetrachlorobenzenediolato)phosphate(V)) anion were quite more effective than their PF6- analogues (x 7.3). A general lack of diastereoselectivity (de

  本文报道了对固有手性假轮烷的立体选择性合成的研究。可以从五个正二价正丙基-1,13-二甲氧基喹ac啶鎓阳离子的外消旋或对映纯（M或P）盐制备手性铵线。它们与DB24C8或双对称取向的DB24C8F6环的自组装形成假轮烷，如1H和19F NMR光谱以及MS测量所示。确定了缔合常数（Ka）。铵抗衡离子在穿线过程中发挥了至关重要的作用，这进一步证明了TRISPHAT（三（四氯苯二醇基）磷酸（V））阴离子的盐比其PF6-类似物（x 7.3）更有效。一般缺乏非对映选择性（de
• Self-Adaptable Catalysts:  Substrate-Dependent Ligand Configuration
  作者：Raivis Zalubovskis、Alexis Bouet、Ester Fjellander、Samuel Constant、David Linder、Andreas Fischer、Jérôme Lacour、Timofei Privalov、Christina Moberg

  DOI：10.1021/ja074044k

  日期：2008.2.1

  Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers C-s conformation in both eta(3)-1,3-diphenylpropenyl and eta(3)-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C-2 and pseudo-C-s symmetric ligands.