[2-(1,3,2-Benzodioxaborol-2-yl)phenyl]-diphenylphosphane | 1442460-65-2

• 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: [2-(1,3,2-Benzodioxaborol-2-yl)phenyl]-diphenylphosphane
• CAS: 1442460-65-2
• 化学式: C₂₄H₁₈BO₂P
• 分子量: 380.19
• InChiKey: LTNIGZDOUCRMSP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.61
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  二氧化碳 、 [2-(1,3,2-Benzodioxaborol-2-yl)phenyl]-diphenylphosphane 在 儿萘酚硼烷 作用下， 以 氘代苯 为溶剂， 反应 48.0h， 生成 5,5-Diphenylspiro[3-oxa-5-phosphonia-2-boranuidabicyclo[4.4.0]deca-1(10),6,8-triene-2,8'-7,9-dioxa-8-boranuidabicyclo[4.3.0]nona-1,3,5-triene]
  参考文献：
  名称：

  使用受挫的路易斯对将 CO2 还原为甲醇：关于膦 - 硼烷介导的 CO2 硼氢化反应的机理

  摘要：

  使用计算和实验方法确定了高活性两亲性有机催化剂 1-Bcat-2-PPh2-C6H4（Bcat = 邻苯二酚）对 CO2 进行硼氢化的完整机制。分子内路易斯对被证明参与了逐步还原的每一步。与传统的受挫路易斯对系统相比，路易斯碱性片段周围没有空间位阻允许还原剂活化，而活性中心的中等路易斯酸度/碱度通过释放还原产物促进催化。还原剂和二氧化碳的同时活化是每个还原步骤中有效催化的关键。

  DOI：

  10.1021/ja5047846
• 作为产物：
  描述：

  (2-(diphenylphosphino)phenyl)lithiumdiethyl etherate 以 四氢呋喃 、 甲苯 为溶剂， 反应 27.0h， 生成 [2-(1,3,2-Benzodioxaborol-2-yl)phenyl]-diphenylphosphane
  参考文献：
  名称：

  A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO₂ to Methanol Using Hydroboranes

  摘要：

  In this work, we report that organocatalyst 1-Bcat-2-PPh2-C6H4 ((1); cat = catechol) acts as an ambiphilic metal-free system for the reduction of carbon dioxide in presence of hydroboranes (HBR2 = HBcat (catecholborane), HBpin (pinacolborane), 9-BBN (9-borabicyclo[3.3.1]nonane), BH3 center dot SMe2 and BH3 center dot THF) to generate CH3OBR2 or (CH3OBO)(3), products that can be readily hydrolyzed to methanol. The yields can be as high as 99% with exclusive formation of CH3OBR2 or (CH3OBO)(3) with TON (turnover numbers) and TOF (turnover frequencies) reaching >2950 and 853 h(-1), respectively. Furthermore, the catalyst exhibits "living" behavior: once the first loading is consumed, it resumes its activity on adding another loading of reagents.

  DOI：

  10.1021/ja404585p
• 作为试剂：
  描述：

  对溴苯甲醛 、 儿萘酚硼烷 在 [2-(1,3,2-Benzodioxaborol-2-yl)phenyl]-diphenylphosphane 作用下， 以 氘代苯 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  使用受挫的路易斯对将 CO2 还原为甲醇：关于膦 - 硼烷介导的 CO2 硼氢化反应的机理

  摘要：

  使用计算和实验方法确定了高活性两亲性有机催化剂 1-Bcat-2-PPh2-C6H4（Bcat = 邻苯二酚）对 CO2 进行硼氢化的完整机制。分子内路易斯对被证明参与了逐步还原的每一步。与传统的受挫路易斯对系统相比，路易斯碱性片段周围没有空间位阻允许还原剂活化，而活性中心的中等路易斯酸度/碱度通过释放还原产物促进催化。还原剂和二氧化碳的同时活化是每个还原步骤中有效催化的关键。

  DOI：

  10.1021/ja5047846

文献信息

• Ring-opening of Epoxides Mediated by Frustrated Lewis Pairs
  作者：Tetiana Krachko、Emmanuel Nicolas、Andreas W. Ehlers、Martin Nieger、J. Chris Slootweg

  DOI：10.1002/chem.201801909

  日期：2018.8.27

  studies, the mechanism of these reactions was found to proceed via activation of the epoxide by the Lewis acidic borane moiety followed by nucleophilic attack of the phosphine of a second FLP molecule. The resulting chain‐like intermediates afford the final cyclic products by ring‐closure and concurrent release of the second equivalent of FLP that behaves as catalyst in this reaction.

  用2-甲基环氧乙烷，2-苯基环氧乙烷和2-甲基环氧乙烷处理t Bu 2 PCH 2 BPh 2（1）和o- Ph 2 P（C 6 H 4）BCat（Cat = catechol）（4） 2-（三氟甲基）环氧乙烷导致环氧化物开环，分别生成六元和七元杂环2 a – c和5 a – c。这些两性离子产物进行光谱表征，和化合物2，图2b，5和通过单晶X射线结构分析对5 c进行了结构表征。基于计算和动力学研究，发现这些反应的机理是通过路易斯酸性硼烷部分激活环氧化物，然后亲核攻击第二个FLP分子的膦来进行的。最终的链状中间体通过闭环并同时释放第二个等效的FLP（在该反应中起催化剂作用）而提供最终的环状产物。
• Trapping of Difluorocarbene by Frustrated Lewis Pairs
  作者：Vladimir O. Smirnov、Alexander D. Volodin、Alexander A. Korlyukov、Alexander D. Dilman

  DOI：10.1002/anie.202001354

  日期：2020.7.20

  Frustrated Lewis pairs consisting of diphenylphosphino and boryl groups located at the ortho‐position can trap difluorocarbene affording stable zwitterionic adducts. The reaction can be reversed to release difluorocarbene at elevated temperatures.

  由位于邻位的二苯基膦基和硼基组成的沮丧的Lewis对可以捕获二氟卡宾，提供稳定的两性离子加合物。该反应可以在升高的温度下逆转以释放出二氟卡宾。
• Hydroboration of Carbon Dioxide Using Ambiphilic Phosphine–Borane Catalysts: On the Role of the Formaldehyde Adduct
  作者：Richard Declercq、Ghenwa Bouhadir、Didier Bourissou、Marc-André Légaré、Marc-André Courtemanche、Karine Syrine Nahi、Nicolas Bouchard、Frédéric-Georges Fontaine、Laurent Maron

  DOI：10.1021/acscatal.5b00189

  日期：2015.4.3

  Ambiphilic phosphine borane derivatives 1-B(OR)(2)-2-PR'(2) C6H4 (R' = Ph (1), iPr (2); (OR)(2) = (OMe)(2) (1a, 2a); catechol (1b, 2h) pinacol (1c, 2c), OCH2C-(CH3)(2)CH2O- (1d)) were tested as catalysts for the hydroboration of CO2 using HBcat or BH3 center dot SMe2 to generate methoxyboranes. It was shown that the most active species were the catechol derivatives 1b and 2b. In the presence of HBcat, without CO2, arnbiphilic species 1a, 1c, and 1d were shown to transform to 1b, whereas 2a and 2c were shown to transform to 2b. The formaldehyde adducts 1b-CH2O and 2b. CH2O are postulated to be the active catalysts in the reduction of CO2 rather than being simple resting states. Isotope labeling experiments and density functional theory (DFT) studies show that once the formaldehyde adduct is generated, the CH2O moiety remains on the ambiphilic system through catalysis. Species 2b center dot CH2O was shown to exhibit turnover frequencies for the CO2 reduction using BH3 center dot SMe2 up to 228 h' at ambient temperature and up to 873 h(-1) at 70 degrees C, mirroring the catalytic activity of 1b.
• A Tris(triphenylphosphine)aluminum Ambiphilic Precatalyst for the Reduction of Carbon Dioxide with Catecholborane
  作者：Marc-André Courtemanche、Jérémie Larouche、Marc-André Légaré、Wenhua Bi、Laurent Maron、Frédéric-Georges Fontaine

  DOI：10.1021/om400645s

  日期：2013.11.25

  The ambiphilic species Al(C6H4(o-PPh2))(3) (2) was synthesized and fully characterized, notably using X-ray diffraction. Species 2 exhibits pseudo-bipyramidal-trigonal geometry caused by the two Al-P interactions. 2 reacts with CO2 to generate a CO2 adduct commonly observed in the activation of CO2 using frustrated Lewis pairs (FLPs). This ambiphilic species serves as a precatalyst for the reduction of CO2 in the presence of catecholborane (HBcat) to generate CH(3)OBcat, which can be readily hydrolyzed in methanol. The reaction mixture confirms that, in the presence of HBcat, 2 generates the known CO2 reduction catalyst 1-Bcat-2-PPh2-C6H4 (1) and intractable catecholate aluminum species. It was, however, possible to isolate a single crystal of Al(kappa O-2,O-(MeO)(2)Bcat)(3) (5) supporting this hypothesis. Also, a borane-protected analogue of 2, Al(C6H4(o-PPh2 center dot BH3))(3) (4), does not react with catecholborane, suggesting the influence of the pendant phosphines in the transformation of 2 into 1.