<2-<(phenylthio)methyl>allyl>trimethylsilane | 116279-69-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: <2-<(phenylthio)methyl>allyl>trimethylsilane
• 英文别名: 3-(Phenylthio)-2-<(trimethylsilyl)methyl>prropene；3-(Phenylthio)-2-<(trimethylsilyl)methyl>propene；2-methylene-3-trimethylsilylpropyl phenyl sulfide；3-phenylthio-2-(trimethylsilylmethyl)-prop-1-ene；3-phenylthio-2-(trimethylsilylmethyl)propene；Trimethyl-[2-(phenylsulfanylmethyl)prop-2-enyl]silane
• CAS: 116279-69-7
• 化学式: C₁₃H₂₀SSi
• 分子量: 236.453
• InChiKey: JSJOKMNARVBZSM-UHFFFAOYSA-N

物化性质

• 沸点：
  285.2±33.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.67
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  <2-<(phenylthio)methyl>allyl>trimethylsilane 在 四氯化钛 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 3-Methoxy-1-phenyl-5-phenylsulfanylmethyl-hex-5-en-1-ol
  参考文献：
  名称：

  [3 + 3]通过连续两个电子和一个电子烯丙基化的环

  摘要：

  3-苯硫基-2-（三甲基甲硅烷基甲基）丙烯是通过[3 + 3]环合法制备亚甲基环己烷的方便的辅助试剂。三甲基甲硅烷基可促进路易斯酸催化的醛或乙缩醛的烯丙基化，而苯硫基可指导6-内-trig自由基环化反应。

  DOI：

  10.1016/s0040-4039(00)92100-2
• 作为产物：
  描述：

  2-[(三甲基硅烷基)甲基]-2-丙烯-1-醇 在 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 <2-<(phenylthio)methyl>allyl>trimethylsilane
  参考文献：
  名称：

  [3 + 3]通过连续两个电子和一个电子烯丙基化的环

  摘要：

  3-苯硫基-2-（三甲基甲硅烷基甲基）丙烯是通过[3 + 3]环合法制备亚甲基环己烷的方便的辅助试剂。三甲基甲硅烷基可促进路易斯酸催化的醛或乙缩醛的烯丙基化，而苯硫基可指导6-内-trig自由基环化反应。

  DOI：

  10.1016/s0040-4039(00)92100-2

文献信息

• The cerium (III) mediated reaction of trimethylsilylmethyl magnesium chloride with esters and lactones: The efficient synthesis of some functionalised allylsilanes of use in annulation reactions
  作者：Thomas V. Lee、Julia A. Channon、Carmel Cregg、John R. Porter、Frances S. Roden、Helena T-L. Yeoh

  DOI：10.1016/s0040-4020(01)89114-6

  日期：1989.1

  (111) chloride alters the chemoselectivity of the reaction of trimethylsilylmethyl magnesium chloride with ester-acetals and also greatly improves the efficiency of reaction with lactones. In addition it gives improved preparations of the useful intermediates (7), (13), (18),(20) and (22) and gives direct access to the valuable functionalised allylsilanes (1) to (3) of use in annulation reactions.

  氯化铈（111）的使用改变了三甲基甲硅烷基甲基氯化镁与酯-缩醛的反应的化学选择性，并且还大大提高了与内酯的反应效率。此外，它提供了有用的中间体（7），（13），（18），（20）和（22）的改进制备方法，并提供了直接用于环化反应的有价值的官能化烯丙基硅烷（1）至（3）的方法。 。
• The diastereoselective synthesis of (+)-actinobolin from D-glucose
  作者：Dale E. Ward、Brian F. Kaller

  DOI：10.1016/0040-4039(93)85088-e

  日期：1993.1

  [3+3] annulation of a D-galactosamine derivative with 3-phenylthio-2- (trimethylsilylmethyl)propene. Formation of the lactone and acylation with L- alanine according to literature precedent gave (+)-actinobolin.

  放线菌素的碳环是通过D-半乳糖胺衍生物与3-苯硫基-2-（三甲基甲硅烷基甲基）丙烯的[3 + 3]环化而构建的。根据文献先例，形成内酯并用L-丙氨酸酰化得到（+）-肌动蛋白。
• Allylation with Pummerer-generated substituted vinylthionium ions
  作者：Roger Hunter、Joseph P. Michael、Clive D. Simon、Daryl S. Walter

  DOI：10.1016/s0040-4020(01)85513-7

  日期：——

  Pummerer-derived substituted vinylthionium ions (allyl phenyl sulfoxide, TMSOFf, EtN(i-Pr)(2), CH2Cl2, -78 degrees C) with a beta-trimethylsilylmethyl (2), gamma-phenyl (14), or gamma-phenylthio (15) group allylate the enol silyl ethers of acetophenone (3) and cyclohexanone (4) in good yield. Allylation with (14) and (15) required slow addition of base in order to limit the rate of production of intermediate, and thus avoid unwanted sila-Pummerer type products. Hunig's base conjugate addition was not observed in these cases. Both the (E)- and (Z)- forms of allyl sulfoxide (15) were shown to equilibrate to the (E)-transoid conformer prior to allylation resulting in exclusive (E)-vinyl sulfide formation. Blocking of the gamma-position resulted in preferential alpha- attack.
• The scope of a new masked Michael reaction involving a Pummerer intermediate
  作者：Roger Hunter、Clive D. Simon

  DOI：10.1016/s0040-4039(00)86726-x

  日期：——
• [3 + 3] Annulation Based on 6-Endo-Trig Radical Cyclization: Regioselectivity and Diastereoselectivity
  作者：Dale E. Ward、Yuanzhu Gai、Brian F. Kaller

  DOI：10.1021/jo00129a024

  日期：1995.12

  The development of a [3 + 3] annulation strategy based on sequential ''two-electron'' and ''one-electron'' allylation of beta-substituted aldehydes and derivatives with the bifunctional isobutene conjunctive reagent 1 is described. The key step involves an unusual 6-endo-trig radical cyclization. Yields of 6-endo products are improved if the PhS group is oxidized to a PhSO(2) group prior to cyclization. The structural factors affecting the regioselectivity and stereoselectivity of the cyclization are examined. In general, the stereoselectivity of 6-endo-trig cyclization of 5-hexenyl radicals can be rationalized by conformational analysis of chairlike transition states and can be calculated effectively with an MM2 force field model, High 6-endo regioselectivity requires a strong driving force. Fragmentable allylic groups (R(3)Sn, PhSO(2), and to a lesser extent PhS) are shown to be sufficiently activating to achieve 6-endo regioselectivity.