(E/Z)-dimethyl(1-methyl-1-propenyl)phenylsilane | 156518-26-2

• 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: (E/Z)-dimethyl(1-methyl-1-propenyl)phenylsilane
• 英文别名: 4-(phenyldimethylsilyl)but-2-ene；But-2-en-2-yl-dimethyl-phenylsilane
• CAS: 156518-26-2
• 化学式: C₁₂H₁₈Si
• 分子量: 190.36
• InChiKey: WXUBJYRZQONXHN-UHFFFAOYSA-N

物化性质

• 沸点：
  232.6±9.0 °C(predicted)
• 密度：
  0.87±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  (E/Z)-dimethyl(1-methyl-1-propenyl)phenylsilane 在 sodium tetrahydroborate 、 氧气 、 rose bengal 作用下， 生成 (±)-2-(dimethylphenylsilyl)-1-buten-3-ol
  参考文献：
  名称：

  Highly Regio- and Diastereoselective One-Pot Synthesis of Silyl Epoxy Alcohols and Vinylsilanes by Direct Hydroxy-Epoxidation

  摘要：

  A direct synthesis of silyl epoxy alcohols from vinyl silanes is described. It consists of the regioselective ene reaction of the vinylsilanes with singlet oxygen, which proceeds with predominant hydrogen abstraction at the position geminal to the silyl group. The resulting silyl allylic hydroperoxides were treated, without isolation, subsequently with Ti(O-i-Pr)(4) to afford the silyl epoxy alcohols in good yields and very high diastereomeric ratios, which ranged from 93:7 to greater than 97:3. Alternatively, the vinylsilanes were photooxygenated directly in the presence of the titanium catalyst and the silyl epoxy alcohols obtained in good yields. The method was applied to di- and trisubstituted acyclic vinylsilanes with a methyl group geminal to silicon and cyclic derivatives all give consistently good results. In this novel hydroxy-epoxidation, the regioselectivity of the singlet oxygen ene reaction as well as the diastereoselectivity of the oxygen transfer can be controlled by the steering effects of the silyl group.

  DOI：

  10.1021/jo00091a021
• 作为产物：
  描述：

  2-溴-2-丁烯 、 苯基二甲基氯硅烷 在 magnesium 作用下， 生成 (E/Z)-dimethyl(1-methyl-1-propenyl)phenylsilane
  参考文献：
  名称：

  A 1,2-silicon shift in cyclopropylidenes leading to 1-trialkylsilylcyclopropenes

  摘要：

  1,1-Dibromo-2-trialkylsilylcyclopropanes, readily prepared by dibromocyclopropanation of vinyltrialkyl-silanes, react with methyllithium at -90 to 20-degrees-C to give high yields of trialkylsilylcyclopropenes in which the silicon has apparently migrated to C-1.

  DOI：

  10.1039/p19930001373
• 作为试剂：
  描述：

  2-((乙氧基碳硫代)硫代)乙酸乙酯 、 (1-methyl-2-propenyl)dimethylphenylsilane 在 苯磺酰基叠氮化物 、 di-tert-butoxydiazene 、 六正丁基二锡 、 (E/Z)-dimethyl(1-methyl-1-propenyl)phenylsilane 作用下， 以 苯 为溶剂， 生成 ethyl syn-4-azido-5-[dimethyl(phenyl)silyl]hexanoate 、 ethyl anti-4-azido-5-[dimethyl(phenyl)silyl]hexanoate
  参考文献：
  名称：

  手性烯丙基硅烷的碳叠氮化：实验和理论研究。

  摘要：

  通过改变硅中心和碳骨架上取代基的性质，研究了手性烯丙基硅烷的碳叠氮化。考虑了温度和磺酰叠氮化物的性质以及偏远的立体生成中心的立体化学对过程的1,2-非对映体控制的影响。通常观察到良好至优异的非对映异构控制水平，其中总是形成顺-β-叠氮基硅烷作为主要异构体。通过短而有效地合成粟精胺类似物提供了这种方法的价值的例证。EPR光谱学是在各种β-甲硅烷基上进行的，提供了有关其基态构象的有用信息。根据这些实验证据和DFT计算，

  DOI：

  10.1002/chem.200701401

文献信息

• One-Pot Synthesis of α-Trimethylsilyl Enones from Vinylsilanes
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1055/s-1994-25433

  日期：——

  Photooxygenation of vinylsilanes in the presence of acetic anhydride and pyridine afforded α-trimethylsilyl enones 1 in moderate to good yields. Since the required starting materials are readily available, the present approach constitutes a useful alternative to existing methods for the preparation of α-trimethylsilyl enones 1.

  在乙酸酐和吡啶的存在下，通过乙烯基硅烷的光氧化反应可以中等至良好的产率获得α-三甲基硅基烯酮1。由于所需的起始材料易于获得，因此本方法为现有制备α-三甲基硅基烯酮1的方法提供了一个有用的替代方案。
• Highly regio - and diastereoselective synthesis of epoxy alcohols directly from vinyl silanes by photo-oxygenation and titanium-catalyzed oxygen transfer
  作者：Waldemar Adam、Markus Richter

  DOI：10.1016/s0040-4039(00)92663-7

  日期：1992.6

  The photooxygenation of vinyl silanes 1 in the presence of Ti(OiPr)4 afforded
• Regioselectivity of the Singlet Oxygen Ene Reaction (Schenck Reaction) with Vinylsilanes
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a020

  日期：1994.6

  The ene reaction-of singlet oxygen and vinylsilanes 1 with various substitution patterns and double-bond geometry has been studied. beta-Silyl allylic hydroperoxides 2 were the major products of the photooxygenation, accompanied by smaller amounts of alpha,beta-unsaturated ketones 3. The latter derive from decomposition of the regioisomeric alpha-hydroperoxy silanes 4 by elimination of silanol. Regioselectivities up to 97:3 were observed for vinylsilanes with a methyl group geminal to the silyl group and with cyclic derivatives. Z-Configurated substrates showed lower regioselectivity and reactivity. Elongation of the carbon chain at the geminal position also increased the amount enone formed. These results are rationalized in terms of stereoelectronic effects imposed by the silyl group on the ring-opening of the perepoxide intermediate.
• Adam, Waldemar; Richter, Markus, Chemische Berichte, 1992, vol. 125, # 1, p. 243 - 246
  作者：Adam, Waldemar、Richter, Markus

  DOI：——

  日期：——