diisopropylphenyl-2-propenylsilane | 152361-78-9

• 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: diisopropylphenyl-2-propenylsilane
• 英文别名: allyldiisopropylphenylsilane；Phenyl-di(propan-2-yl)-prop-2-enylsilane
• CAS: 152361-78-9
• 化学式: C₁₅H₂₄Si
• 分子量: 232.441
• InChiKey: QZWDSXXQYHYVCS-UHFFFAOYSA-N

物化性质

• 沸点：
  286.0±19.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.35
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  diisopropylphenyl-2-propenylsilane 在 四氟硼酸-二乙醚络合物 、 氯化锆(IV) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 26.5h， 生成 (2S,4S)-4-(Fluoro-diisopropyl-silanyl)-2-phenyl-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Stereoselective synthesis of cyclopentanols by Lewis acid-mediated [3+2] annulation of allyldiisopropylphenylsilane with α,β-unsaturated diesters

  摘要：

  ZrCl4-mediated annulation of allyldiisopropylphenylsilane with alpha,beta-unsaturated diesters and subsequent oxidative cleavage of the carbon-silicon bond furnished cyclopentanols highly stereoselectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01748-1
• 作为产物：
  描述：

  二异丙基氯代硅烷 在 bis(triphenylphosphine)nickel(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 433.0h， 生成 diisopropylphenyl-2-propenylsilane
  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

• Allyldiisopropylphenylsilane as a synthetic equivalent of 2-hydroxy-1,3-dipole. Stereoselective synthesis of cyclopentanols
  作者：Takahiko Akiyama、Eriko Hoshi、Satoru Fujiyoshi

  DOI：10.1039/a804118k

  日期：——

  ZrCl4-Promoted [3 + 2] cycloaddition of allyldiisopropylphenylsilane to α,β-unsaturated ketones proceeds smoothly to afford silyl-substituted cyclopentanes highly stereoselectively. Oxidative cleavage of the carbon–silicon bond leads to stereoselective formation of cyclopentanols.

  ZrCl4促进的烯丙基二异丙基苯基硅烷与α,β-不饱和酮的[3 + 2]环加成反应顺利进行，高度立体选择性地得到硅基取代的环戊烷。通过氧化断裂碳-硅键，可以立体选择性地形成环戊醇。
• Mechanistic Study on the Base-Promoted Reaction of Allylphenylsilanes to Alkenylsilanols
  作者：Shigeaki Imazeki、Hiroo Sugawara、Atsunori Sano、Takahiko Akiyama

  DOI：10.1246/bcsj.81.623

  日期：2008.5.15

  substitution of the phenyl group with a hydroxy group took place smoothly to afford alkenylsilanol derivatives in good yields. The reaction mechanism was investigated using 18 O-labeled sulfoxide. We found that a (methylsulfinyl)methyl anion generated from DMSO participated in this reaction.

  在 DMSO 中用 t-BuOK 和 18-crown-6 处理烯丙基苯基硅烷时，烯烃双键的异构化和随后的苯基被羟基取代的过程顺利进行，以良好的产率得到烯基硅烷醇衍生物。使用 18 O-标记的亚砜研究了反应机理。我们发现由 DMSO 产生的（甲基亚磺酰基）甲基阴离子参与了该反应。
• Base Promoted Preparation of Alkenylsilanols from Allylsilanes
  作者：Takahiko Akiyama、Shigeaki Imazeki

  DOI：10.1246/cl.1997.1077

  日期：1997.10

  On treatment of allyl-t-butyldiphenylsilane with t-BuOK and 18-Crown-6 in DMSO at room temperature, isomerization of the olefinic double bond and subsequent substitution of phenyl group with hydroxy group took place smoothly to afford alkenylsilanol derivatives in good yields.

  在室温下用DMSO对烯丙基-t-丁基二苯基硅烷进行t-BuOK和18-冠-6的处理，烯烃双键发生异构化，随即用羟基取代苯基，顺利合成了产率良好的烯基硅醇衍生物。
• Carbocyclization Reaction of Malonate Derivatives with Allylsilane Moiety Mediated by AlCl₃-<i>n</i>-Bu₃N
  作者：Shigeaki Imazeki、Ryohiko Kinoshita、Takahiko Akiyama

  DOI：10.1246/bcsj.80.972

  日期：2007.5.15

  Allylsilane bearing malonate moiety underwent intramolecular carbocyclization reaction by means of AlCl3-n-Bu3N to give silyl-substituted cyclopentanes in good yields.

  带有丙二酸酯部分的烯丙基硅烷通过AlCl3-n-Bu3N进行分子内碳环化反应，以良好的收率得到甲硅烷基取代的环戊烷。
• An Unprecedented Domino Double Allylsilane [3+2] Cycloaddition/Wagner-Meerwein Rearrangement/Friedel-Crafts Alkylation/Elimination Reaction Sequence Leading to a Novel Pentacyclic Ring System
  作者：Hans-Joachim Knölker、Elke Baum、Regina Graf、Peter G. Jones、Oliver Spieß

  DOI：10.1002/(sici)1521-3773(19990903)38:17<2583::aid-anie2583>3.0.co;2-1

  日期：1999.9.3

  A stereoselective synthesis of the disilyl derivatives 3 is achieved by the title reaction, an unprecedented Lewis acid promoted domino reaction, between the cross-conjugated dienone 1 and the allylsilanes 2. The configurations of the five stereogenic centers of this novel ring system are established in the first step of the reaction sequence, the double [3+2] cycloaddition.

  通过标题反应，前所未有的路易斯酸促进的多米诺反应，在交叉共轭二烯酮1和烯丙基硅烷2之间实现了二甲硅烷基衍生物3的立体选择性合成。反应顺序的第一步是双[3 + 2]环加成反应。