dimethyl (2-(diphenylphosphaneyl)phenyl)boronate | 1318802-31-1

• 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: dimethyl (2-(diphenylphosphaneyl)phenyl)boronate
• CAS: 1318802-31-1
• 化学式: C₂₀H₂₀BO₂P
• 分子量: 334.162
• InChiKey: WMRCTCNLJBMSID-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.43
• 重原子数：
  24.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  dimethyl (2-(diphenylphosphaneyl)phenyl)boronate 以 甲苯 为溶剂， -78.0~80.0 ℃ 、202.66 kPa 条件下， 反应 16.0h， 生成
  参考文献：
  名称：

  Hydroboration of Carbon Dioxide Using Ambiphilic Phosphine–Borane Catalysts: On the Role of the Formaldehyde Adduct

  摘要：

  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.

  DOI：

  10.1021/acscatal.5b00189
• 作为产物：
  描述：

  硼酸三甲酯 、 (2-(diphenylphosphino)phenyl)lithiumdiethyl etherate 以 四氢呋喃 为溶剂， 生成 dimethyl (2-(diphenylphosphaneyl)phenyl)boronate
  参考文献：
  名称：

  单重态双氧与膦-硼烷衍生物的反应：从瞬时过氧化膦到结晶过硼硼酸盐

  摘要：

  在温和的条件下，单线态双氧很容易被膦-硼酸酯分解。最初形成的过氧化膦通过B→O迁移自发地重排。所得到的过氧硼酸酯已经进行了结构表征，并且证实了它们进行氧转移反应的能力。

  DOI：

  10.1002/anie.201000520

文献信息

• A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO₂ to Methanol Using Hydroboranes
  作者：Marc-André Courtemanche、Marc-André Légaré、Laurent Maron、Frédéric-Georges Fontaine

  DOI：10.1021/ja404585p

  日期：2013.6.26

  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.