(E/Z)-1-methyl-1-propenyltrimethylsilane | 10111-13-4

• 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)-1-methyl-1-propenyltrimethylsilane
• 英文别名: (E)-1-methyl-1-propenyltrimethylsilane；2-Trimethylsilyl-buten-(2)；trimethyl-(1-methyl-propenyl)-silane；2-Trimethylsilyl-but-2-en；Trimethyl-(1-methyl-propenyl)-silan；Silane, trimethyl(1-methyl-1-propenyl)-, (E)-；[(E)-but-2-en-2-yl]-trimethylsilane
• CAS: 10111-13-4
• 化学式: C₇H₁₆Si
• 分子量: 128.29
• InChiKey: QOZLCBPYZLFNST-VOTSOKGWSA-N

物化性质

• 沸点：
  110 °C
• 密度：
  0.740±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.83
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  (E/Z)-1-methyl-1-propenyltrimethylsilane 在 吡啶 、 4-二甲氨基吡啶 、 5E-4 M TPP 、 氧气 、 乙酸酐 作用下， 以 乙酸甲酯 为溶剂， 反应 4.5h， 以49%的产率得到3-(三甲基硅烷基)-3-丁烯-2-酮
  参考文献：
  名称：

  One-Pot Synthesis of α-Trimethylsilyl Enones from Vinylsilanes

  摘要：

  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。

  DOI：

  10.1055/s-1994-25433
• 作为产物：
  描述：

  三甲基氯硅烷 、 2-chloro-2-butene 生成 (E/Z)-1-methyl-1-propenyltrimethylsilane
  参考文献：
  名称：

  硅化合碳二铂络合物：（二）。硅烷反应，CH 2 = CH（CH 2）n SiMe 3（n = 0，1 et 2）

  摘要：

  快速配位是乙烯基-，烯丙基-和丁-3-烯-1-基-三甲基硅烷与二毛钱[Pt 2 Cl 4（C 2 H 4）2 ]之间反应的第一步。接下来是裂解前两个硅烷的活化的SC键。讨论了给出该反应的Pt（II）配合物的性质，以及它们与质子酸活性的比较。结果表明，丁-2-烯-2-基三甲基硅烷的SiC（sp 2）键的裂解是立体定向的。

  DOI：

  10.1016/s0022-328x(00)89684-9

文献信息

• Conversion of some alkenyltrimethylsilanes into silyl enol ethers
  作者：Robert F. Cunico

  DOI：10.1016/s0022-328x(00)85675-2

  日期：1981.6

  The cycloaddition products (5-trimethylsilylisoxazolines) between alkenyltrimethylsilanes and acetonitrile oxide undergo thermolytic rearrangement-cycloreversion to afford silyl enol ethers of retained stereochemistry vs. the starting alkenylsilanes.

  烯基三甲基硅烷和乙腈氧化物之间的环加成产物（5-三甲基甲硅烷基恶唑啉）进行热解重排-环还原，得到相对于起始烯基硅烷而言保留立体化学的甲硅烷基烯醇醚。
• On the origin of geminal regioselectivity in the ene reaction of singlet oxygen with substituted alkenes
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1016/s0040-4039(00)61349-7

  日期：1993.1

  The geminal regioselectivity observed in the ene reaction between singlet oxygen and alkenes with anion-stabilizing groups is rationalized on the basis of a perepoxide intermediate, in which in analogy to the nucleophilic attack on protonated epoxides, the perepoxide is opened preferentially at the CO bond weakened by the substituent.

  在单线态氧与带有阴离子稳定基团的烯烃之间的烯反应中观察到的双晶区域选择性是基于过氧化物中间体进行合理化的，其中类似于质子化环氧化物的亲核攻击，过氧化物优选在C = O处打开被取代基削弱的键。
• 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.
• Highly Regio- and Diastereoselective One-Pot Synthesis of Silyl Epoxy Alcohols and Vinylsilanes by Direct Hydroxy-Epoxidation
  作者：Waldemar Adam、Markus J. Richter

  DOI：10.1021/jo00091a021

  日期：1994.6

  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.
• Formation of α-silylvinyllithium reagents: Reactions of α-silyl- and α-stannyl-vinyllithiums with aldehydes and ketones
  作者：Terence N. Mitchell、Werner Reimann

  DOI：10.1016/0022-328x(85)87105-9

  日期：1985.2