4,4,5,5‐tetramethyl‐2‐(5‐phenylpent‐1‐ynyl)‐1,3,2‐dioxaborolane | 178693-05-5

• 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: 4,4,5,5‐tetramethyl‐2‐(5‐phenylpent‐1‐ynyl)‐1,3,2‐dioxaborolane
• 英文别名: 4,4,5,5-Tetramethyl-2-(5-phenylpent-1-ynyl)-1,3,2-dioxaborolane
• CAS: 178693-05-5
• 化学式: C₁₇H₂₃BO₂
• 分子量: 270.179
• InChiKey: ACZDFUWCXNFSEZ-UHFFFAOYSA-N

物化性质

• 沸点：
  329.3±35.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.64
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  4,4,5,5‐tetramethyl‐2‐(5‐phenylpent‐1‐ynyl)‐1,3,2‐dioxaborolane 在 HZrCp₂Cl 、 CuBr 、 NH₄Cl 作用下， 以 四氢呋喃 、 水 为溶剂， 以65%的产率得到2-[(4E,6E)-1,10-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)deca-4,6-dien-5-yl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Zirconocene-Mediated Preparation of 1,3-, 1,4-, and 2,3-Dibora-1,3-butadienes:  Their Isolation and Characterization and Use in Suzuki−Miyaura Coupling

  摘要：

  Hydrozirconation of 1-alkynyl pinacolboronates, 1, with HZrCp(2)Cl provides gem-borazirconocenes 2. The latter when treated with CuBr gives the homocoupled (1E,3E)-2,3-dibora-1,3-butadienes, 3, in good yield (62-67%). The reaction works even for hindered 2 (R = t-Bu). Structure 3 was assigned on the basis of NMR. Suzuki-Miyaura coupling of 3a (R = n-Bu) with PhI in the presence of CsF leads to the replacement of both boron groups by phenyl and hydrogen to give 6 in 76% yield. Zirconocene-mediated coupling of 1 leads to diastereomeric products: (1E,3E)-1,3-dibora-1,3-butadienes, 4, in 7-26% isolated yields and (1E,3E)-1,4-dibora-1,3-butadienes, 5, in 17-34% isolated yields. The two isomers can be separated by selective precipitation of 5 from the reaction mixture in pentane (-20 degrees C) followed by silica gel chromatography to give pure 4. The reaction does not work when R in 1 is the t-Bu group. Assignments of structures for 4 and 5 were done on the basis of 1D and 2D NMR experiments. In addition, a single-crystal X-ray analysis of 5a showed it to be a highly planar and linearly oriented molecule. Suzuki-Miyaura coupling of 4a proceeded to replace the terminal boron group exclusively, while the internal boron group of 4a remained intact.

  DOI：

  10.1021/om960178n
• 作为产物：
  描述：

  异丙醇频哪醇硼酸酯 、 5-苯基-1-戊炔 在 正丁基锂 作用下， 以 乙醚 为溶剂， 生成 4,4,5,5‐tetramethyl‐2‐(5‐phenylpent‐1‐ynyl)‐1,3,2‐dioxaborolane
  参考文献：
  名称：

  铜催化亚胺的立体选择性烯化

  摘要：

  催化维蒂希型烯化反应的新视角。我们探索了使用过渡金属催化从容易获得的起始材料形成叶立德等价物，从而开发出以烯基硼酸酯作为偶联伙伴的高E选择性铜催化亚胺烯化反应。

  DOI：

  10.1002/anie.202316521

文献信息

• Iron(II)-Catalyzed Trifluoromethylation of Potassium Vinyltrifluoroborates
  作者：Andrew T. Parsons、Todd D. Senecal、Stephen L. Buchwald

  DOI：10.1002/anie.201108267

  日期：2012.3.19

  2‐heteroarylvinyl‐substituted substrates with E/Z selectivities of more than 95:5. Experimental observations suggest that the reaction does not proceed through a transmetalation of the RBF3K species to the iron catalyst.

  用CF 3交换BF 3 ：标题反应在极其温和的反应条件下进行，并提供2-芳基乙烯基-和2-杂芳基乙烯基-取代的底物，其E / Z选择性大于95:5。实验观察表明，该反应不是通过 RBF 3 K 物质向铁催化剂的金属转移来进行的。