3-[(tert-butyl)(dimethyl)silanyloxy]-2-methylidene-5-phenylpentanol | 845508-86-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-[(tert-butyl)(dimethyl)silanyloxy]-2-methylidene-5-phenylpentanol
• 英文别名: 3-[Tert-butyl(dimethyl)silyl]oxy-2-methylidene-5-phenylpentan-1-ol
• CAS: 845508-86-3
• 化学式: C₁₈H₃₀O₂Si
• 分子量: 306.521
• InChiKey: CGLBOXFBMZBFGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.56
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-[(tert-butyl)(dimethyl)silanyloxy]-2-methylidene-5-phenylpentanol 在 Grubbs catalyst first generation 、 草酰氯 、 双(三甲基硅烷基)氨基钾 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 氘代苯 为溶剂， -78.0~30.0 ℃ 、689.47 kPa 条件下， 生成 (tert-butyl)(dimethyl)(2-methylidene-1-phenethyl-but-3-enyloxy)silane
  参考文献：
  名称：

  Equilibrium Control in Enyne Metathesis:  Crossover Studies and the Kinetic Reactivity of (E,Z)-1,3-Disubstituted-1,3-Dienes

  摘要：

  The stereoselectivity of diene bond formation in the ruthenium-carbene mediated intermolecular enyne metathesis was studied. Initial reaction between an alkyne and 1-hexene gave mixtures of E- and Z-isomers in the newly formed 1,3-diene. However, over time the mixtures equilibrated to form mostly the diene of the E-configuration. To evaluate individual reactivity of the E- and Z-dienes, they were independently synthesized. The E-diene was found to be kinetically-stable under nominal metathesis conditions while the Z-diene isomerized to the E-isomer. The Z-isomeric dienes were found to react with other alkenes to produce a new diene of E-configuration. A secondary metathesis mechanism involving ruthenium alkylidene intermediates was invoked to explain the dynamic stereochemistry observed in this study.

  DOI：

  10.1021/jo0482209
• 作为产物：
  描述：

  (3-Hydroxy-2-methylidene-5-phenylpentyl) acetate 在 咪唑 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 3-[(tert-butyl)(dimethyl)silanyloxy]-2-methylidene-5-phenylpentanol
  参考文献：
  名称：

  Equilibrium Control in Enyne Metathesis:  Crossover Studies and the Kinetic Reactivity of (E,Z)-1,3-Disubstituted-1,3-Dienes

  摘要：

  The stereoselectivity of diene bond formation in the ruthenium-carbene mediated intermolecular enyne metathesis was studied. Initial reaction between an alkyne and 1-hexene gave mixtures of E- and Z-isomers in the newly formed 1,3-diene. However, over time the mixtures equilibrated to form mostly the diene of the E-configuration. To evaluate individual reactivity of the E- and Z-dienes, they were independently synthesized. The E-diene was found to be kinetically-stable under nominal metathesis conditions while the Z-diene isomerized to the E-isomer. The Z-isomeric dienes were found to react with other alkenes to produce a new diene of E-configuration. A secondary metathesis mechanism involving ruthenium alkylidene intermediates was invoked to explain the dynamic stereochemistry observed in this study.

  DOI：

  10.1021/jo0482209

文献信息

• Stereoselective and Diversity-Oriented Synthesis of Trisubstituted Allylic Alcohols and Amines
  作者：Yvonne Schmidt、Bernhard Breit

  DOI：10.1002/chem.201100844

  日期：2011.10.10

  reagent‐directing o‐DPPB group, copper‐mediated allylic substitution with a wide range of Grignard reagents enabled the stereoselective construction of a large number of E‐configured trisubstituted allylic alcohols and amines in excellent yields and stereoselectivities. Remarkable is the synthetic flexibility, which allows a wide range of permutations starting from an aldehyde followed by successive introduction

  三取代烯烃的立体选择性和多样性取向合成是通过使用邻二苯基膦基苯甲酸苯酯（o- DPPB）作为烯丙基取代的指导基团来实现的。这种方法的出发点是衍生自Baylis-Hillman加合物的一组α-亚甲基醛。随后添加不同的有机金属试剂产生了多种烯丙基醇底物。引入试剂导向的o -DPPB基团后，用多种格氏试剂进行铜介导的烯丙基取代使多种E的立体选择性构建成为可能。预配置的三取代烯丙基醇和胺，具有出色的收率和立体选择性。显着的是合成柔性，其允许从醛开始的宽范围的排列，然后从有机金属格氏试剂连续引入取代基R 2和R 3。因此，仅从少数几种前体开始，就可以实现立体定向的三取代烯丙基醇和胺的多样化导向合成。