(R)-2,2'-bis(3-methoxyphenyl)-1,1'-binaphthalene | 820974-49-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-2,2'-bis(3-methoxyphenyl)-1,1'-binaphthalene
• 英文别名: 2,2'-Bis(3-methoxyphenyl)-1,1'-binaphthalene；2-(3-methoxyphenyl)-1-[2-(3-methoxyphenyl)naphthalen-1-yl]naphthalene
• CAS: 820974-49-0
• 化学式: C₃₄H₂₆O₂
• 分子量: 466.579
• InChiKey: MXPDDFOUAYCGLQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.2
• 重原子数：
  36
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  (R)-2,2'-bis(3-methoxyphenyl)-1,1'-binaphthalene 在 三溴化硼 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到(S)-3,3'-(1,1'-binaphthalene-2,2'-diyl)bisphenol
  参考文献：
  名称：

  Bisphenylene homologues of BINOL-based phosphoramidites: synthesis, stereostructure, and application in catalysis

  摘要：

  Bis-ortho- and bis-meta-phenylene homologues of BINOL-based N,N-dimethylphosphoramidites were prepared from the corresponding diols by treatment with hexamethyltriaminophosphane. Phosphoramidites derived from bulkier secondary amines were synthesized by 5-phenyl-1H-tetrazole-promoted amine exchange. All the phosphoramidites were obtained as single diastereomers. Their configurations at the C(naphthyl)-C(phenyl) axes were determined by vibrational circular dichroism (VCD) spectroscopy. Preliminary testing of the ligands in copper-catalyzed conjugate addition of diethylzinc to acyclic enones and nitrostyrene gave the corresponding products in up to 74% ee. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.02.041
• 作为产物：
  描述：

  1,1'-binaphthalene-2,2'-diyldiboronic acid 在 四(三苯基膦)钯 barium dihydroxide 、 三溴化硼 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 68.0h， 生成 (R)-2,2'-bis(3-methoxyphenyl)-1,1'-binaphthalene
  参考文献：
  名称：

  Novel Route to Enantiopure 2,2'-Diaryl-1,1'-binaphthalenes by Stereoconservative Suzuki Arylation at Positions 2 and 2'

  摘要：

  对手性纯的2,2'-二碘-1,1'-联萘进行银促芳基化反应，可以得到2,2'-二芳基化产物，收率相当可观（高达52%），但会发生明显的拉仑化。采用反向极性方法，使用新型的手性纯1,1'-联萘-2,2'-二基硼酸，通过拆分或立体保持硼化反应制备，经过偶联条件的优化，可以获得模型2,2'-二对甲苯基化产物同样有良好的收率（56%），同时不影响对映体纯度（即立体保持）。这种合成方法被发现是一种方便的方法，特别适用于合成手性纯的2,2'-二芳基-1,1'-联萘，尤其适用于带有电子中性和电子亏缺的芳基团。观察到硼酸在反应条件下通过氢去硼反应分解，与反应性较差的电子富集芳基碘发生反应时，主要产物是2-芳基-1,1'-联萘。

  DOI：

  10.1135/cccc20041517

文献信息

• Deracemization of Binaphthyl by Suzuki Diarylation: The Role of Electronic and Steric Effects
  作者：Filip Bulko、Michal Májek、Martin Putala

  DOI：10.1021/acs.joc.2c01041

  日期：2022.7.15

  factors that are investigated and found to affect the stereoselective course of the reaction include the reaction temperature, palladium source, palladium to ligand ratio, and the type of boronic acid derivative. During the chromatographic separation of diarylated products on an achiral silica gel, we observed a rare phenomenon: the diarylated products undergo self-disproportionation of enantiomers, with

  我们报告了外消旋 2,2'-diiodo-1,1'-binaphthyl 的 Suzuki 2,2'-二芳基化反应，通过一个简单的手性配体─BINAP [2, 2'-双(二苯基膦基)-1,1',-联萘]。使用 45 种芳基硼酸对反应范围的系统研究表明，二芳基化产物是在间位和/或对位时形成的-取代的苯基硼酸被具有从-0.5到+0.4的哈米特常数的取代基官能化。使用玻尔兹曼加权 Sterimol 参数和 Hammett 描述符描述的电子效应对几何形状对反应性影响的多参数分析表明，对映选择性仅取决于空间效应，对于具有较大长度wL的取代基观察到增强的对映选择性，并减少最大宽度wB 5较大的取代基. 我们表明，借助所提出的数学模型，仔细调整这些参数可以产生出色的对映选择性。研究并发现影响反应立体选择性过程的其他因素包括反应温度、钯源、钯与配体的比例以及硼酸衍生物的类型。在非手性硅胶上二芳基化产物的色
• Novel Route to Enantiopure 2,2'-Diaryl-1,1'-binaphthalenes by Stereoconservative Suzuki Arylation at Positions 2 and 2'
  作者：Henrich Brath、Margaréta Dubovská、Michal Juríček、Peter Kasák、Martin Putala

  DOI：10.1135/cccc20041517

  日期：——

  The Suzuki arylation of enantiopure 2,2'-diiodo-1,1'-binaphthalene affords the 2,2'-diarylated products in considerable yields (up to 52%), however, significantly racemized. The reversed-polarity approach, using novel enantiopure 1,1'-binaphthalene-2,2'-diyldiboronic acid, prepared either by resolution or by stereoconservative boronation, allowed, after optimization of coupling conditions, to obtain the model 2,2'-ditolylated product in good yield (56%) as well, but in addition, without impairing of enantiomeric purity (i.e. stereoconservatively). The developed synthetic approach was found to be an expedient method for the synthesis of enantiopure 2,2'-diaryl-1,1'-binaphthalenes, especially for those with electron-neutral and electron-deficient poor aryl groups. Observing that the diboronic acid decomposes by hydrodeboronation under the reaction conditions, 2-aryl-1,1'-binaphthalenes were isolated as the main products from the reaction with less reactive electron-rich aryl iodides.

  对手性纯的2,2'-二碘-1,1'-联萘进行银促芳基化反应，可以得到2,2'-二芳基化产物，收率相当可观（高达52%），但会发生明显的拉仑化。采用反向极性方法，使用新型的手性纯1,1'-联萘-2,2'-二基硼酸，通过拆分或立体保持硼化反应制备，经过偶联条件的优化，可以获得模型2,2'-二对甲苯基化产物同样有良好的收率（56%），同时不影响对映体纯度（即立体保持）。这种合成方法被发现是一种方便的方法，特别适用于合成手性纯的2,2'-二芳基-1,1'-联萘，尤其适用于带有电子中性和电子亏缺的芳基团。观察到硼酸在反应条件下通过氢去硼反应分解，与反应性较差的电子富集芳基碘发生反应时，主要产物是2-芳基-1,1'-联萘。
• Bisphenylene homologues of BINOL-based phosphoramidites: synthesis, stereostructure, and application in catalysis
  作者：Natalia Miklášová、Ondřej Julínek、Michaela Mešková、Vladimír Setnička、Marie Urbanová、Martin Putala

  DOI：10.1016/j.tetlet.2010.02.041

  日期：2010.4

  Bis-ortho- and bis-meta-phenylene homologues of BINOL-based N,N-dimethylphosphoramidites were prepared from the corresponding diols by treatment with hexamethyltriaminophosphane. Phosphoramidites derived from bulkier secondary amines were synthesized by 5-phenyl-1H-tetrazole-promoted amine exchange. All the phosphoramidites were obtained as single diastereomers. Their configurations at the C(naphthyl)-C(phenyl) axes were determined by vibrational circular dichroism (VCD) spectroscopy. Preliminary testing of the ligands in copper-catalyzed conjugate addition of diethylzinc to acyclic enones and nitrostyrene gave the corresponding products in up to 74% ee. (C) 2010 Elsevier Ltd. All rights reserved.