sodium tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate dihydrate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: sodium tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate dihydrate
• 英文别名: Sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate xhydrate；sodium;tetrakis[3,5-bis(trifluoromethyl)phenyl]boranuide;hydrate
• 化学式: C₃₂H₁₂BF₂₄*2H₂O*Na
• 分子量: 922.24
• InChiKey: HWQYENOITDMKQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.39
• 重原子数：
  59
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  26

反应信息

• 作为反应物：
  描述：

  sodium tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate dihydrate 以 solid 为溶剂， 生成 四(3,5-二(三氟甲基)苯基)硼酸钠
  参考文献：
  名称：

  Safe Preparation and Purification of Sodium Tetrakis[(3,5-trifluoromethyl)phenyl]borate (NaBArF₂₄):  Reliable and Sensitive Analysis of Water in Solutions of Fluorinated Tetraarylborates

  摘要：

  A safe, convenient preparation of the reagent sodium tetrakis[(3,5-trifluoromethyl)phenyl]borate (NaBArF24) has been devised by utilizing a magnesium-bromine exchange reaction in the absence of metallic magnesium. Purified material was then rigorously dried over P2O5 (NaBArF24 with < 500 ppm H2O by mass) or recrystallized as a hydrate (NaBArF24 center dot(2.6 +/- 0.1)H2O). Accurate analysis of the water content of these samples by H-1 NMR was accomplished by using dimethylzirconocene (Cp2Zr(CH3)(2)).

  DOI：

  10.1021/om0501428
• 作为产物：
  描述：

  氟硼酸钠 、 3,5-双三氟甲基溴苯 在 Mg 、 dibromoethane 作用下， 以 乙醚 为溶剂， 以90%的产率得到sodium tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate dihydrate
  参考文献：
  名称：

  Control of the Stereochemical Impact of the Lone Pair in Lead(II) Tris(pyrazolyl)methane Complexes. Improved Preparation of Na{B[3,5-(CF₃)₂C₆H₃]₄}

  摘要：

  The reaction of Pb(acac)(2) with 2 equiv of [H(Et2O)(2)]{B[3,5-(CF3)(2)C6H3]4} (HBArf) in CH2Cl2 followed by addition of 2 equiv of either HC(pz)(3) or HC(3,5-Me(2)pz)(3) (pz = pyrazolyl ring) leads to the formation of {Pb[HC(pz)(3)](2)}-{B[3,5-(CF3)(2)C6H3](4)}(2) (1) and {Pb[HC(3,5-Me(2)pz)(3)](2)}{B [3,5-(CF3)(2)C6H3](4)}(2) (2), respectively. The cation in 1 has a distorted octahedral structure with a stereochemically active lone pair on lead(II). In contrast, the cation in 2 is trigonally distorted octahedral with the lone pair on the lead(II) clearly stereochemically inactive. The driving force for this cation to have a stereochemically inactive lone pair is that in this geometric arrangement the interligand distances between adjacent 3-position methyl groups are close to 4.0 Angstrom, the sum of the van der Waals radii of two methyl groups. To facilitate this chemistry, the synthesis of Na{B [3,5-(CF3)(2)C6H3](4)}, needed to prepare HBArf, has been dramatically improved. The main change is to add NaBF4 to the reaction mixture before forming the Grignard from the reaction of magnesium and 3,5-(CF3)(2)C6H3Br. The Grignard reacts with the NaBF4 as it forms, reducing the danger of explosion and leading to a higher isolated yield of the product. Crystallographic information: 1 is triclinic, P (1) over bar, a 13.0133(6) Angstrom, b = 17.2210(7) Angstrom, c = 24.7634(11) Angstrom, alpha = 71.7300(10)degrees, beta = 82.3630(10)degrees, gamma = 70.5120(10)degrees, Z = 2; 2 is triclinic, P (1) over bar, a = 12.756(4) Angstrom, b = 13.469(4) Angstrom, c = 17.160(5) Angstrom, alpha = 82.454(7)degrees, beta = 89.904(8)degrees, gamma = 72.995(7)degrees Z = 1.

  DOI：

  10.1021/ic0100121
• 作为试剂：
  描述：

  a-叠氮基-苯乙酸甲酯 、 间苯二甲醚 在 iron(III) chloride 、 1,10-菲罗啉 、 sodium tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate dihydrate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 8.0h， 以70%的产率得到methyl 2-(2,4-dimethoxyphenyl)-2-phenylacetate
  参考文献：
  名称：

  铁催化的α-芳基-α-重氮酯的芳基化†

  摘要：

  开发了铁催化的α-芳基-α-重氮酸酯与富电子苯环的芳基化反应，这为高产率，优异的化学选择性和区域选择性提供了一种制备1,1-二芳基乙酸酯的有效方法。

  DOI：

  10.1039/c5ob02418h

文献信息

• Diastereo- and Enantioselective Synthesis of Fluorine Motifs with Two Contiguous Stereogenic Centers
  作者：Sudipta Ponra、Wangchuk Rabten、Jianping Yang、Haibo Wu、Sutthichat Kerdphon、Pher G. Andersson

  DOI：10.1021/jacs.8b08778

  日期：2018.10.24

  motifs, in particular, chiral fluorine molecules with two contiguous stereogenic centers, has attracted much interest in research due to the limited number of methods available for their preparation. Herein, we report an atom-economical and highly stereoselective synthesis of chiral fluorine molecules with two contiguous stereogenic centers via azabicyclo iridium-oxazoline-phosphine-catalyzed hydrogenation

  手性氟的合成，特别是具有两个连续立体中心的手性氟分子，由于其制备方法的数量有限，引起了人们对研究的极大兴趣。在此，我们报告了通过氮杂双环铱-恶唑啉-膦催化氢化容易获得的氟乙烯，以原子经济和高度立体选择性合成具有两个连续立体中心的手性氟分子。发现具有各种官能团的各种芳香族、脂肪族和杂环系统与反应相容，并提供非常理想的产物，作为具有优异对映选择性的单一非对映异构体。
• Room temperature and solvent-free iridium-catalyzed selective alkylation of anilines with alcohols
  作者：Jia-Qi Li、Pher G. Andersson

  DOI：10.1039/c3cc42669f

  日期：——

  A bidentate iridium NHC–phosphine complex has been developed and applied to the N-monoalkylation of aromatic amines with a wide range of primary alcohols and to the N-heterocyclization of amino alcohols. This reaction resulted in high isolated product yields, even at room temperature and under solvent-free conditions.

  一种双齿铱NHC-膦配体复合物已被开发并应用于广泛范围的伯醇与芳香胺的N-单烷基化反应和氨基酸醇的N-杂环化。该反应在室温下和无溶剂条件下均能产生高分离产物收率。
• Combined Theoretical and Experimental Studies Unravel Multiple Pathways to Convergent Asymmetric Hydrogenation of Enamides
  作者：Jianping Yang、Luca Massaro、Suppachai Krajangsri、Thishana Singh、Hao Su、Emanuele Silvi、Sudipta Ponra、Lars Eriksson、Mårten S. G. Ahlquist、Pher G. Andersson

  DOI：10.1021/jacs.1c09573

  日期：2021.12.29

  We present a highly efficient convergent asymmetric hydrogenation of E/Z mixtures of enamides catalyzed by N,P–iridium complexes supported by mechanistic studies. It was found that reduction of the olefinic isomers (E and Z geometries) produces chiral amides with the same absolute configuration (enantioconvergent hydrogenation). This allowed the hydrogenation of a wide range of E/Z mixtures of trisubstituted

  我们提出了一种由 N,P-铱配合物催化的E / Z烯酰胺混合物的高效收敛不对称氢化，并得到机理研究的支持。发现烯烃异构体（E和Z几何形状）的还原产生具有相同绝对构型的手性酰胺（对映收敛氢化）。这允许以优异的对映选择性（高达 99% ee）。使用氘标记和动力学实验的详细机理研究揭示了观察到的对映收敛的两种不同途径。对于 α-芳基烯酰胺，双键发生快速异构化，整个过程导致两种异构体的动力学拆分。对于 α-烷基烯酰胺，没有检测到双键异构化，竞争实验表明底物螯合是对映收敛立体化学结果的原因。进行 DFT 计算以预测产物的正确绝对构型并加强提出的铱催化异构化途径的机制。
• Well-Defined Chiral Spiro Iridium/Phosphine−Oxazoline Cationic Complexes for Highly Enantioselective Hydrogenation of Imines at Ambient Pressure
  作者：Shou-Fei Zhu、Jian-Bo Xie、Yong-Zhen Zhang、Shen Li、Qi-Lin Zhou

  DOI：10.1021/ja063444p

  日期：2006.10.1

  catalyze the hydrogenation of acyclic N-aryl ketimines under ambient pressure with excellent enantioselectivities (up to 97% ee) and full conversions. This result represents the highest enantioselectivity and the first example of the hydrogenation of imines catalyzed by chiral analogues of the Crabtree catalyst at ambient pressure. Studies on the stability of the catalysts revealed that the catalysts Ir-SIPHOX

  从光学纯的 7-diphenylphosphino-7'-trifluoromethanesulfonyloxyl-1,1'-spirobindane 开始，分四步合成了具有刚性和庞大螺二茚烷支架的新型手性膦-恶唑啉配体（7，SIPHOX），总含量为 40-64%屈服。铱配合物 7，Crabtree 催化剂的手性类似物，是通过配体 7 和 [Ir(COD)Cl](2) 在 tetrakis-3,5-bis(trifluoromethyl)phenylborate 钠存在下的配位生成的。通过NMR、ESI-MS和X-射线衍射分析表征配合物。Ir-SIPHOX 配合物可以在环境压力下催化无环 N-芳基酮亚胺的氢化，具有出色的对映选择性（高达 97% ee）和完全转化。该结果代表了最高的对映选择性和在环境压力下由 Crabtree 催化剂的手性类似物催化的亚胺氢化的第一个例子。对催化剂稳定性的研究表明，Ir-SIPHOX
• Activation of a Carbon–Carbon Bond in Internal Alkynes: Vinylidene Rearrangement of Disubstituted Alkynes at an Ir Complex
  作者：Youichi Ishii、Takuya Kuwabara、Shuhei Takamori、Satoshi Kishi、Takahiro Watanabe、Yousuke Ikeda、Shintaro Kodama、Yasunori Minami、Tamejiro Hiyama

  DOI：10.1055/s-0036-1591511

  日期：2018.4

  [Cp*Ir(PPh3)Cl2] with various internal acyl­alkynes in the presence of NaBArF 4 resulted in the selective formation of iridacycles via vinylidene rearrangement. 13C-labeling experiments revealed that the acyl group selectively migrates to the other acetylenic carbon atom. This trend is the same as that in the vinylidene rearrangement of internal alkynes at a group 8 metal center.

  [Cp*Ir(PPh3)Cl2] 与各种内部炔烃在 NaBArF 4 存在下的反应导致通过亚乙烯基重排选择性地形成虹膜环。13C 标记实验表明酰基选择性地迁移到另一个炔属碳原子。这种趋势与内部炔烃在第 8 族金属中心的亚乙烯基重排中的趋势相同。