二烯丙基二异丙基硅烷 | 10519-89-8

• 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
• 中文名称: 二烯丙基二异丙基硅烷
• 英文名称: diallyldiisopropylsilane
• 英文别名: Di(propan-2-yl)-bis(prop-2-enyl)silane
• CAS: 10519-89-8
• 化学式: C₁₂H₂₄Si
• 分子量: 196.408
• InChiKey: IQFIVIPGQWMWGM-UHFFFAOYSA-N

物化性质

• 沸点：
  210.0±9.0 °C(Predicted)
• 密度：
  0.775±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.63
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  二烯丙基二异丙基硅烷 在 potassium fluoride 、 三氟化硼乙醚 、 双氧水 、 potassium hydrogencarbonate 、 丁烯酮 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 6-[(Hydroxy-diisopropyl-silanyl)-methyl]-non-8-en-2-one
  参考文献：
  名称：

  Lewis acid mediated domino allylation of diallylsilane to α,β-unsaturated ketones

  摘要：

  在BF3·OEt2处理二烯丙基二异丙基硅烷和α,β-不饱和酮时，烯丙基部分的1,4-加成和随后的分子内烯丙基化作用会生成β-硅基碳正离子中间体，进而得到多米诺烯丙基化产物。通过碳-硅键的氧化断裂，可以高收率地得到双高烯丙醇。

  DOI：

  10.1039/a807640e
• 作为产物：
  描述：

  二异丙基二氯硅烷 、 氯丙烯镁 在 苯基氯化镁 作用下， 生成 diisopropylphenyl-2-propenylsilane 、 二烯丙基二异丙基硅烷
  参考文献：
  名称：

  Highly Stereoselective Synthesis of Bicyclo[n.3.0]alkanes by Titanium Tetrachloride Promoted [3 + 2] Cycloaddition of Allylsilanes and 1-Acetylcycloalkenes

  摘要：

  AbstractThe titanium tetrachloride promoted reaction of allylsilanes 1 with 1‐acetylcyclohexene is shown to afford the silylbicyclo[4.3.0]nonanes 9 ([3 + 2] cycloaddition products) along with the 1‐acetyl‐2‐allylcyclohexane 4 (Hosomi‐Sakurai product). Here we report that systematic variation of the substituents at the silicon atom of 1 allows suppression of the classical Hosomi‐Sakurai reaction in favor of the [3 + 2] cycloaddition. Cycloaddition of the allylsilanes 1 d, 1 i, and 1 k with 1‐acetylcycloalkenes 10, containing a 5‐, 6‐, 7‐, 8‐, or 12‐membered ring, gives rise to the corresponding silylbicyclo[n.3.0]alkanes 11 – 13. The cycloaddition of allyltriisopropylsilane (1 k) and 1‐acetyl‐2‐methylcycloalkenes 15 provides silylbicyclo[n.3.0]alkanes 16 with two contiguous quaternary carbon centers. The stereochemistry of the silylbicyclo[n.3.0]alkanes 11 a ‐ c and 14 is unambiguously determined by X‐ray analysis and 13C NMR spectroscopy.

  DOI：

  10.1002/chem.19970030409

文献信息

• Iodine-mediated rearrangements of diallylsilanes
  作者：Gregory W. O'Neil、Elizabeth J. Cummins

  DOI：10.1016/j.tetlet.2017.07.045

  日期：2017.8

  Diallylsilanes can be made to rearrange upon treatment with I2. Of the silanes tested, diallyldiphenylsilane showed the greatest propensity to undergo this intramolecular carbocation allylation process. After etherification of the initially formed iodosilane, the products from this transformation represent useful synthetic intermediates, suitable for alkylation and cross-metathesis/annulation reactions

  可以使二烯丙基硅烷在用I 2处理后重新排列。在测试的硅烷中，二烯丙基二苯基硅烷显示出进行这种分子内碳阳离子烯丙基化过程的最大可能性。最初形成的碘硅烷醚化后，该转化产物代表有用的合成中间体，适用于烷基化和复分解/环化反应。
• Tandem Cyclization/Hydroarylation of α,ω-Dienes Triggered by Scandium-Catalyzed C–H Activation
  作者：Bin Tang、Xiaoyan Hu、Chunli Liu、Tao Jiang、Fakhre Alam、Yanhui Chen

  DOI：10.1021/acscatal.8b04713

  日期：2019.1.4

  regio- and diastereoselective cyclization/hydroarylation reaction of 1,5- and 1,6-dienes with aromatic ethers and tertiary anilines was established by a cationic 2-picoline-tethered-half-sandwich scandium alkyl catalyst, which constitutes a process for producing a diverse array of cis-1,3-disubstituted arylated and trans-1,2-disubstituted benzylated methylcyclopentane derivatives in one step with 100% atom-efficiency

  1，5-和1，6-二烯与芳族醚和叔苯胺的高度区域和非对映选择性环化/氢芳基化反应是通过阳离子2-甲基吡啶系留的半三明治s烷基烷基催化剂建立的，一步以100％的原子效率生产多种顺式-1,3-二取代的芳基化和反式-1,2-二取代的苄基化甲基环戊烷衍生物。此外，还提出了涉及involving催化的芳族邻-C-H活化和烯烃插入级联反应的机理。
• Highly Stereoselective Synthesis of Bicyclo[n.3.0]alkanes by Titanium Tetrachloride Promoted [3 + 2] Cycloaddition of Allylsilanes and 1-Acetylcycloalkenes
  作者：Hans-Joachim Knölker、Norbert Foitzik、Helmut Goesmann、Regina Graf、Peter G. Jones、Günter Wanzl

  DOI：10.1002/chem.19970030409

  日期：1997.4

  AbstractThe titanium tetrachloride promoted reaction of allylsilanes 1 with 1‐acetylcyclohexene is shown to afford the silylbicyclo[4.3.0]nonanes 9 ([3 + 2] cycloaddition products) along with the 1‐acetyl‐2‐allylcyclohexane 4 (Hosomi‐Sakurai product). Here we report that systematic variation of the substituents at the silicon atom of 1 allows suppression of the classical Hosomi‐Sakurai reaction in favor of the [3 + 2] cycloaddition. Cycloaddition of the allylsilanes 1 d, 1 i, and 1 k with 1‐acetylcycloalkenes 10, containing a 5‐, 6‐, 7‐, 8‐, or 12‐membered ring, gives rise to the corresponding silylbicyclo[n.3.0]alkanes 11 – 13. The cycloaddition of allyltriisopropylsilane (1 k) and 1‐acetyl‐2‐methylcycloalkenes 15 provides silylbicyclo[n.3.0]alkanes 16 with two contiguous quaternary carbon centers. The stereochemistry of the silylbicyclo[n.3.0]alkanes 11 a ‐ c and 14 is unambiguously determined by X‐ray analysis and 13C NMR spectroscopy.
• Lewis acid mediated domino allylation of diallylsilane to α,β-unsaturated ketones
  作者：Takahiko Akiyama、Kanae Asayama、Satoru Fujiyoshi

  DOI：10.1039/a807640e

  日期：——

  On treatment of diallyldiisopropylsilane and α,β-unsaturated ketones with BF3·OEt2, 1,4-addition of an allyl moiety and subsequent intramolecular allylation onto the β-silyl carbocation intermediate furnished domino allylation products. Oxidative cleavage of the carbon–silicon bond furnished bis-homoallylic alcohols in good yields.

  在BF3·OEt2处理二烯丙基二异丙基硅烷和α,β-不饱和酮时，烯丙基部分的1,4-加成和随后的分子内烯丙基化作用会生成β-硅基碳正离子中间体，进而得到多米诺烯丙基化产物。通过碳-硅键的氧化断裂，可以高收率地得到双高烯丙醇。