Trimethyl-octa-6,7-dien-1-ynyl-silane | 168209-24-3

• 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-octa-6,7-dien-1-ynyl-silane
• CAS: 168209-24-3
• 化学式: C₁₁H₁₈Si
• 分子量: 178.349
• InChiKey: NWARSFWYEWUBJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.38
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  一氧化碳 、 Trimethyl-octa-6,7-dien-1-ynyl-silane 在 di(rhodium)tetracarbonyl dichloride 作用下， 以 甲苯 为溶剂， 90.0 ℃ 、101.33 kPa 条件下， 以45%的产率得到3-Trimethylsilanyl-5,6-dihydro-1H,4H-inden-2-one
  参考文献：
  名称：

  An Allenic Pauson−Khand-Type Reaction:  A Reversal in π-Bond Selectivity and the Formation of Seven-Membered Rings

  摘要：

  [GRAPHICS]Treatment of alkynyl allenes with [Rh(CO)(2)Cl](2) results in a formal [2 + 2 + 1] cycloaddition reaction. This reaction occurs with complete regioselectivity for a variety of substrates affording only 4-alkylidene cyclopentenones in good yields. Moreover, seven-membered rings have been prepared in high yields.

  DOI：

  10.1021/ol025955w
• 作为产物：
  描述：

  5-溴戊-1-炔基(三甲基)硅烷 、 甲基炔丙基醚 在 magnesium 、 copper(I) bromide 作用下， 生成 Trimethyl-octa-6,7-dien-1-ynyl-silane
  参考文献：
  名称：

  一种新的烯丙基Pauson-Khand环加成反应，用于制备α-亚甲基环戊烯酮

  摘要：

  炔基丙二烯经过一个分子内的钼介导的鲍森-汉德环加成反应，一步即可提供官能化的α-亚甲基环戊烯酮。

  DOI：

  10.1016/0040-4039(95)00315-4

文献信息

• A new allenic Pauson-Khand cycloaddition for the preparation of α-methylene cyclopentenones
  作者：Joseph L. Kent、Honghe Wan、Kay M. Brummond

  DOI：10.1016/0040-4039(95)00315-4

  日期：1995.4

  Alkynyl allenes undergo an intramolecular molybdenum-mediated Pauson-Khand cycloaddition to provide functionalized α-methylene cyclopentenones in one step.

  炔基丙二烯经过一个分子内的钼介导的鲍森-汉德环加成反应，一步即可提供官能化的α-亚甲基环戊烯酮。
• An Allenic Pauson−Khand-Type Reaction:  A Reversal in π-Bond Selectivity and the Formation of Seven-Membered Rings
  作者：Kay M. Brummond、Hongfeng Chen、Kimberly D. Fisher、Angela D. Kerekes、Brenden Rickards、Peter C. Sill、Steven J. Geib

  DOI：10.1021/ol025955w

  日期：2002.5.1

  [GRAPHICS]Treatment of alkynyl allenes with [Rh(CO)(2)Cl](2) results in a formal [2 + 2 + 1] cycloaddition reaction. This reaction occurs with complete regioselectivity for a variety of substrates affording only 4-alkylidene cyclopentenones in good yields. Moreover, seven-membered rings have been prepared in high yields.
• 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.