[Me2NH2][Δ-BINPHAT] | 475975-39-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: [Me2NH2][Δ-BINPHAT]
• 英文别名: [dimethylammonium][Δ-BINPHAT]
• CAS: 475975-39-4
• 化学式: C34H20Cl8NO6P
• 分子量: 853.1
• InChiKey: IEFWFHJMQSSQHV-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  14.13
• 重原子数：
  50
• 可旋转键数：
  0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  72
• 氢给体数：
  1
• 氢受体数：
  7

文献信息

• Conformationally-locked metallomacrocycles—prototypes for a novel type of axial chirality
  作者：Hoi Shan Chow、Edwin C. Constable、Richard Frantz、Catherine E. Housecroft、Jérôme Lacour、Markus Neuburger、Dmitrij Rappoport、Silvia Schaffner

  DOI：10.1039/b819588a

  日期：——

  series of ditopic ligands incorporating two 2,2′:6′,2″-terpyridine (tpy) metal-binding domains linked to a central naphthalenediyl core by ethyleneoxy chains of various lengths have been prepared and their iron(II) complexes prepared. The major thermodynamic products of complexation are ferracycles of [1 + 1], [2 + 2] or [3 + 3] stoichiometry. In the case of the [1 + 1] complexes, the linker between

  一系列包含两个2,2'的对位配体：6′，2″-吡啶 （py）通过中央萘二甲酰基核心连接的金属结合域 乙氧基 已经准备好各种长度的链条， 铁（II）配合物准备好了。络合的主要热力学产物是[1 + 1]，[2 + 2]或[3 + 3]化学计量的铁环。对于[1 +1]复合物，两者之间的连接子py区域受到空间限制，阳离子显示出与中心N–Fe–N键构象相关的手性。在手性阴离子存在的情况下，利用Pfeiffer效应通过NMR和圆二色光谱研究了手性阴离子存在时对映体形式相互转化的动力学过程。我们已经证明了双（2,2'：6'，2''-三联吡啶） 配体产生构象受限的配合物 铁（II）中心。通过菲佛效应获得的非对映体离子对中阳离子的绝对构型已使用TDDFT 方法。
• Resolution of the First Nonracemic Diquats
  作者：Jérôme Vachon、Gérald Bernardinelli、Jérôme Lacour

  DOI：10.1002/chem.200902562

  日期：——

  the first configurationally stable derivatives of their kind. Resolution was achieved by using chiral hexacoordinated phosphorus BINPHAT and TRISPHAT anions. The diquat cations were obtained in high diastereo‐ and enantiomeric purity (ee>96 % in most cases). X‐ray diffraction analysis coupled with circular dichroism (CD) measurements allowed a precise determination of the relative and absolute configuration

  制备了三个具有八元环的三环二quat，并证明是同类中第一个构型稳定的衍生物。使用手性六配位磷BINPHAT和TRISPHAT阴离子可实现分离。以高非对映体和对映体纯度（大多数情况下ee > 96％）获得了敌草快阳离子。X射线衍射分析和圆二色性（CD）测量可以精确确定盐的相对和绝对构型。这些化合物外消旋的障碍是通过在不同温度下使用CD时程测量法计算得出的，得出的ΔG ≠值高于25 kcal mol -1。衍生物4，图4b，和4 c是只有三个环约束有待解决的前八元环导数。该手稿还报告了非对映异构体分离后去除TRISPHAT阴离子的第一个步骤。
• Configurational Ordering of Cationic Chiral Dyes Using a Novel <i>C</i>₂-Symmetric Hexacoordinated Phosphate Anion
  作者：Jérôme Lacour、Anne Londez、Catherine Goujon-Ginglinger、Volker Buss、Gérald Bernardinelli

  DOI：10.1021/ol006731l

  日期：2000.12.1

  [GRAPHICS]C-2-Symmetry hexacoordinated phosphorus BINPHAT anion-of configuration controlled by a BINOL ligand-can be prepared readily in a one pot process and behaves as an efficient NMR chiral shift agent and chiral inducer onto monomethinium dyes (CD, H-1 NMR).
• 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.