(E)-2-[(trimethylsilyl)methyl]-6-oxohex-2-enenitrile | 1180510-84-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-2-[(trimethylsilyl)methyl]-6-oxohex-2-enenitrile
• 英文别名: (E)-6-oxo-2-(trimethylsilylmethyl)hex-2-enenitrile
• CAS: 1180510-84-2
• 化学式: C₁₀H₁₇NOSi
• 分子量: 195.337
• InChiKey: ZEBHFHORCBKUFM-UXBLZVDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-(trimethylsilyloxy)-3-butenenitrile 、 炔丙基三甲基硅烷 在 bis(1,5-cyclooctadiene)nickel (0) 、 三(4-三氟甲苯基)膦 、 盐酸 作用下， 以 乙腈 、 四氢呋喃 、 水 为溶剂， 反应 1.0h， 以70%的产率得到(E)-2-[(trimethylsilyl)methyl]-6-oxohex-2-enenitrile
  参考文献：
  名称：

  Nickel-Catalyzed Carbocyanation of Alkynes with Allyl Cyanides

  摘要：

  Allyl cyanides are found to add across alkynes in the presence of a nickel/P(4-CF3-C6H4)(3) catalyst to give polysubstituted 2,5-hexadienenitriles with defined stereo- and regiochemistry. Use of AlMe2Cl or AlMe3 as a Lewis acid cocatalyst accelerates the reaction and expands the substrate scope significantly. The cyano group in the allylcyanation products can be transformed to a hydroxymethyl or aminomethyl group to afford highly substituted allylic alcohols or amines. alpha-Siloxyallyl cyanides also add across alkynes selectively at the less hindered gamma-carbon to allow introduction of 3-oxo-propyl functionality after hydrolysis of the resulting silyl enol ethers. This particular carbocyanation reaction has been applied to the stereoselective construction of the trisubstituted double bond of plaunotol, an antibacterial natural product active against Helicobacter pylori.

  DOI：

  10.1021/ja901374v

文献信息

• Nickel-Catalyzed Carbocyanation of Alkynes with Allyl Cyanides
  作者：Yasuhiro Hirata、Tomoya Yukawa、Natsuko Kashihara、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1021/ja901374v

  日期：2009.8.12

  Allyl cyanides are found to add across alkynes in the presence of a nickel/P(4-CF3-C6H4)(3) catalyst to give polysubstituted 2,5-hexadienenitriles with defined stereo- and regiochemistry. Use of AlMe2Cl or AlMe3 as a Lewis acid cocatalyst accelerates the reaction and expands the substrate scope significantly. The cyano group in the allylcyanation products can be transformed to a hydroxymethyl or aminomethyl group to afford highly substituted allylic alcohols or amines. alpha-Siloxyallyl cyanides also add across alkynes selectively at the less hindered gamma-carbon to allow introduction of 3-oxo-propyl functionality after hydrolysis of the resulting silyl enol ethers. This particular carbocyanation reaction has been applied to the stereoselective construction of the trisubstituted double bond of plaunotol, an antibacterial natural product active against Helicobacter pylori.