Trimethyl-[4-(2-vinylidene-cyclopentyl)-but-1-ynyl]-silane | 203449-20-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Trimethyl-[4-(2-vinylidene-cyclopentyl)-but-1-ynyl]-silane
• CAS: 203449-20-1
• 化学式: C₁₄H₂₂Si
• 分子量: 218.414
• InChiKey: MUXBNGUHDDJCNH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Trimethyl-[4-(2-vinylidene-cyclopentyl)-but-1-ynyl]-silane 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以53%的产率得到1-vinylidene-2-(3-butynyl)cyclopentane
  参考文献：
  名称：

  An Intramolecular Allenic [2 + 2 + 1] Cycloaddition

  摘要：

  A new stereo- and regioselective method for the preparation of alpha-methylene and 4-alkylidene cyclopentenones is described. These substructures were achieved by an intramolecular [2 + 2 + 1] cycloaddition of an allene, alkyne, and carbon monoxide moieties to afford the target compounds stereoselectively and in good yields. In some cases, the target compounds were obtained as mixtures, but it is demonstrated that the formation of either the alpha-methylene or 4-alkylidene cyclopentenone can be controlled by the allene structure or reaction conditions. Monosubstituted allenes afford alpha-methylene cyclopentenones as the only cycloadduct. Disubstitution on the allene alters the course of the allenic [2 + 2 + 1] reaction. 3,3-Disubstituted allenes undergo cycloaddition with the least substituted pi-bond of the allene. This affords the bicyclo[4.3.0]nonane ring system. Cycloaddition of 1,3-disubstituted allenes afford mixtures of several possible cycloadducts. However, it has been shown that good control over the product ratio can be obtained by altering the cycloaddition conditions and that the regiochemistry can be directed depending upon the metal used.

  DOI：

  10.1021/jo980548c
• 作为产物：
  描述：

  4-bromo-1-trimethylsilylbut-1-yne 在 氢化钾 、 copper(l) chloride 、 lithium chloride 、 magnesium chloride 、 manganese(ll) chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 Trimethyl-[4-(2-vinylidene-cyclopentyl)-but-1-ynyl]-silane
  参考文献：
  名称：

  An Intramolecular Allenic [2 + 2 + 1] Cycloaddition

  摘要：

  A new stereo- and regioselective method for the preparation of alpha-methylene and 4-alkylidene cyclopentenones is described. These substructures were achieved by an intramolecular [2 + 2 + 1] cycloaddition of an allene, alkyne, and carbon monoxide moieties to afford the target compounds stereoselectively and in good yields. In some cases, the target compounds were obtained as mixtures, but it is demonstrated that the formation of either the alpha-methylene or 4-alkylidene cyclopentenone can be controlled by the allene structure or reaction conditions. Monosubstituted allenes afford alpha-methylene cyclopentenones as the only cycloadduct. Disubstitution on the allene alters the course of the allenic [2 + 2 + 1] reaction. 3,3-Disubstituted allenes undergo cycloaddition with the least substituted pi-bond of the allene. This affords the bicyclo[4.3.0]nonane ring system. Cycloaddition of 1,3-disubstituted allenes afford mixtures of several possible cycloadducts. However, it has been shown that good control over the product ratio can be obtained by altering the cycloaddition conditions and that the regiochemistry can be directed depending upon the metal used.

  DOI：

  10.1021/jo980548c

文献信息

• The allenic Pauson-Khand cycloaddition. Dependence in π-bond selectivity on substrate structure
  作者：Kay M. Brummond、Honghe Wan

  DOI：10.1016/s0040-4039(97)10679-7

  日期：1998.2

  Alkynyl allenes undergo intramolecular Pauson-Khand (P-K) cycloadditions to provide functionalized α-methylene and 4-alkylidene cyclopentenones in good yields. These studies have demonstrated a dependence of the π-bond selectivity of this cycloaddition on the substitution pattern of the allene.

  炔基丙二烯进行分子内的Pauson-Khand（PK）环加成反应，以高收率提供官能化的α-亚甲基和4-亚烷基环戊烯酮。这些研究已经证明，该环加成的π键选择性依赖于丙二烯的取代模式。
• An Intramolecular Allenic [2 + 2 + 1] Cycloaddition
  作者：Kay M. Brummond、Honghe Wan、Joseph L. Kent

  DOI：10.1021/jo980548c

  日期：1998.9.1

  A new stereo- and regioselective method for the preparation of alpha-methylene and 4-alkylidene cyclopentenones is described. These substructures were achieved by an intramolecular [2 + 2 + 1] cycloaddition of an allene, alkyne, and carbon monoxide moieties to afford the target compounds stereoselectively and in good yields. In some cases, the target compounds were obtained as mixtures, but it is demonstrated that the formation of either the alpha-methylene or 4-alkylidene cyclopentenone can be controlled by the allene structure or reaction conditions. Monosubstituted allenes afford alpha-methylene cyclopentenones as the only cycloadduct. Disubstitution on the allene alters the course of the allenic [2 + 2 + 1] reaction. 3,3-Disubstituted allenes undergo cycloaddition with the least substituted pi-bond of the allene. This affords the bicyclo[4.3.0]nonane ring system. Cycloaddition of 1,3-disubstituted allenes afford mixtures of several possible cycloadducts. However, it has been shown that good control over the product ratio can be obtained by altering the cycloaddition conditions and that the regiochemistry can be directed depending upon the metal used.