1-cyclohexyl-1-hexyn-1-yl-methyl methyl carbonate | 1082069-17-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-cyclohexyl-1-hexyn-1-yl-methyl methyl carbonate
• CAS: 1082069-17-7
• 化学式: C₁₅H₂₄O₃
• 分子量: 252.354
• InChiKey: QJUFKDUIOPQGJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-cyclohexyl-1-hexyn-1-yl-methyl methyl carbonate 、 联硼酸频那醇酯 在 copper (I) tert-butoxide 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成
  参考文献：
  名称：

  Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronates

  摘要：

  A versatile synthetic method for the preparation of the allenylboronates, Cu(I)-catalyzed reaction of propargylic carbonates with a diboron, is described. A Cu(O-t-Bu)-Xantphos catalyst system was effective for the preparation of various allenylboron compounds, allenylboronates with different substitution patterns, those with functional groups, and an axially chiral one. The Lewis acid promoted stereoselective addition to aldehydes leading to homopropargylic alcohols showed the usefulness of the new allenylboronates.

  DOI：

  10.1021/ja806602h
• 作为产物：
  描述：

  1-环己基庚-2-炔-1-醇 、 氯甲酸甲酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 1-cyclohexyl-1-hexyn-1-yl-methyl methyl carbonate
  参考文献：
  名称：

  Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronates

  摘要：

  A versatile synthetic method for the preparation of the allenylboronates, Cu(I)-catalyzed reaction of propargylic carbonates with a diboron, is described. A Cu(O-t-Bu)-Xantphos catalyst system was effective for the preparation of various allenylboron compounds, allenylboronates with different substitution patterns, those with functional groups, and an axially chiral one. The Lewis acid promoted stereoselective addition to aldehydes leading to homopropargylic alcohols showed the usefulness of the new allenylboronates.

  DOI：

  10.1021/ja806602h

文献信息

• Negishi Coupling for Highly Selective Syntheses of Allenes via Ligand Effect and Mechanistic Study via SAESI‐MS/MS
  作者：Yangguangyan Zheng、Bukeyan Miao、Anni Qin、Junzhe Xiao、Qi Liu、Gen Li、Li Zhang、Fang Zhang、Yinlong Guo、Shengming Ma

  DOI：10.1002/cjoc.201900322

  日期：2019.10

  Assisted Electrospray Ionization Mass Spectrometry) has been applied to successfully capture the highly reactive organometallic intermediates, which show the different coordination behaviors of Pd with SPhos or Gorlos‐Phos as the ligand in the catalytic cycle. In addition, the different reactivities of Int 1 and Int 2 towards the formation of the final allene products have been demonstrated via SAESI‐MS/MS

  在过渡金属催化的反应中，β-H的消除是一个固有的问题。我们在此描述了一个有趣的Et 2 Zn分别充当乙基提供者或H提供者的配体效应：通过应用SPhos或Gorlos-Phos作为配体，已成功在相应的Negishi偶联反应中控制了β-H的消除，从而提供了不同的聚预取代的异戊烯，收率高，选择性好。SAESI-MS（š olvent甲ssisted é lectroSPray我onization中号屁股小号光谱法）已成功地捕获了高反应性的有机金属中间体，这些中间体在催化循环中显示出Pd与SPhos或Gorlos-Phos作为配体的不同配位行为。此外，通过SAESI-MS / MS实验证明了Int 1和Int 2对最终丙二烯产物形成的不同反应性。这些质谱研究可视化了Negishi偶联反应的整个催化循环，同时很好地解释了所观察到的反应性和选择性。