4,4,5,5-tetramethyl-2-(4-phenyl-but-1-yn-1-yl)-1,3,2-dioxaborolane | 159087-44-2

• 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: 4,4,5,5-tetramethyl-2-(4-phenyl-but-1-yn-1-yl)-1,3,2-dioxaborolane
• 英文别名: 4,4,5,5-Tetramethyl-2-(4-phenylbut-1-yn-1-yl)-1,3,2-dioxaborolane；4,4,5,5-tetramethyl-2-(4-phenylbut-1-ynyl)-1,3,2-dioxaborolane
• CAS: 159087-44-2
• 化学式: C₁₆H₂₁BO₂
• 分子量: 256.153
• InChiKey: RCNQBTQEQMDOMY-UHFFFAOYSA-N

物化性质

• 沸点：
  313.3±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)：
  3.25
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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-(4-phenyl-but-1-yn-1-yl)-1,3,2-dioxaborolane 以80%的产率得到
  参考文献：
  名称：

  Deloux Laurent, Srebnik Morris, J. Org. Chem, 59 (1994) N 22, S 6871-6873

  摘要：

  DOI：
• 作为产物：
  描述：

  4-苯基-1-丁炔 、 异丙醇频哪醇硼酸酯 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以89%的产率得到4,4,5,5-tetramethyl-2-(4-phenyl-but-1-yn-1-yl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  使用炔基硼酸酯的Pauson-Khand反应：解决长期存在的区域选择性问题

  摘要：

  已经描述了与内部炔基硼酸酯进行的第一分子间Pauson-Khand反应。这种策略允许将硼酸酯部分安装在环戊烯酮的b位上，总的...

  DOI：

  10.1039/c6cc04717c

文献信息

• Catalytic Dehydrogenative Borylation of Terminal Alkynes by a SiNN Pincer Complex of Iridium
  作者：Chun-I Lee、Jia Zhou、Oleg V. Ozerov

  DOI：10.1021/ja311682c

  日期：2013.3.6

  catalytic dehydrogenative borylation of carbon-hydrogen bonds with dialkoxyboranes (RO)2BH is particularly attractive. It has been demonstrated for a variety of carbon-hydrogen bond types but not for the C(sp)-H bonds of terminal alkynes, for which hydroboration of the triple bond is a competing process. We report a new iridium catalyst that is strictly chemoselective for C-H borylation of terminal alkynes

  具有碳硼键的化合物是通用中间体，可通过将碳硼键加工成其他碳元素键来构建更复杂的分子。通过碳-氢键与二烷氧基硼烷 (RO)2BH 的催化脱氢硼酸化合成碳-硼键特别有吸引力。它已被证明适用于各种碳氢键类型，但不适用于末端炔烃的 C(sp)-H 键，因此三键的硼氢化是一个竞争过程。我们报告了一种新的铱催化剂，它对末端炔烃的 CH 硼酸化具有严格的化学选择性。这种催化剂成功的关键似乎是新的辅助 SiNN 钳配体，它结合了酰胺基、喹啉和甲硅烷基供体，并产生结构上不寻常的 Ir 配合物。
• Synthesis of Triborylalkenes from Terminal Alkynes by Iridium-Catalyzed Tandem CH Borylation and Diboration
  作者：Chun-I Lee、Wei-Chun Shih、Jia Zhou、Joseph H. Reibenspies、Oleg V. Ozerov

  DOI：10.1002/anie.201507372

  日期：2015.11.16

  reaction to convert terminal alkynes into triborylalkenes is reported. In the first step, the terminal alkyne and pinacolborane (HBpin) are converted into an alkynylboronate, which is catalyzed by an iridium complex supported by a SiNN pincer ligand. In the second step, treatment of the reaction mixture with CO generates a new catalyst which mediates dehydrogenative diboration of alkynylboronate with

  报道了将末端炔烃转化为三硼烷基烯烃的两步反应。第一步，将末端炔烃和频哪醇硼烷（HBpin）转化为炔基硼酸酯，然后由SiNN夹钳配体负载的铱配合物催化。在第二步骤中，用CO处理反应混合物产生了新的催化剂，该催化剂介导了频哪醇硼烷对炔基硼酸酯的脱氢二硼化作用。硼氢化作用的机理尚不清楚，但它不是通过硼氢化产物的中间产物或通过B 2 pin 2进行的。
• 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
  作者：Guillaume Desurmont、Rita Klein、Stefan Uhlenbrock、Eric Laloë、Laurent Deloux、Dean M. Giolando、Yong Wah Kim、Schubert Pereira、Morris Srebnik

  DOI：10.1021/om960178n

  日期：1996.7.23

  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.