2,2,4-trimethyl-5-phenyldimethylsilylmethyl-1,2-epoxy-5-hexene | 620176-38-7

• 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: 2,2,4-trimethyl-5-phenyldimethylsilylmethyl-1,2-epoxy-5-hexene
• 英文别名: 2,4,4-trimethyl-5-phenyldimethylsilylmethyl-1,2,-epoxy-5-hexene；[3,3-Dimethyl-2-methylidene-4-(2-methyloxiran-2-yl)butyl]-dimethyl-phenylsilane
• CAS: 620176-38-7
• 化学式: C₁₈H₂₈OSi
• 分子量: 288.505
• InChiKey: XIMLZCSZWZATCG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.36
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2,4-trimethyl-5-phenyldimethylsilylmethyl-1,2-epoxy-5-hexene 在 草酰氯 、 二甲基亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 0.66h， 生成 2,2,4-trimethyl-4-[1-(dimethylphenylsilylmethyl)cyclopropyl]pentanal
  参考文献：
  名称：

  Seven-Membered Ring Formation from Cyclopropanated Oxo- and Epoxyallylsilanes

  摘要：

  A useful strategy for cycloheptane annulations from oxo- and epoxyallylsilanes, prepared by silylcupration of allenes, has been developed, and their application to the stereoselective synthesis of 4-methylenecycloheptan-1-ols is of great potential in the construction of seven-membered ring natural products presented.

  DOI：

  10.1021/jo200705u
• 作为产物：
  描述：

  4-甲基-3戊烯-2-酮 在 正丁基锂 、 锂丁酯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 2,2,4-trimethyl-5-phenyldimethylsilylmethyl-1,2-epoxy-5-hexene
  参考文献：
  名称：

  酸催化的环氧烯丙基硅烷环化反应。一个异常的重排环化过程。

  摘要：

  [反应：请参见文字]。据报道，合成带有苯基二甲基甲硅烷基的环氧烯丙基硅烷的新途径涉及甲硅烷基化丙二烯，将共轭物加成烯酮以及硫代叶立德介导的环氧化。呈现了路易斯酸催化的这些底物的环化。没有观察到源自5-exo和/或6-endo攻击的预期正常产物；而是形成了由串联重排-环化过程产生的亚甲基环己醇。

  DOI：

  10.1021/ol035297v

文献信息

• Synthesis of 3-Methylenecyclohexan-1-ols by Lewis Acid Catalyzed Cyclization of (Epoxy-allyl)silanes
  作者：Francisco J. Pulido、Asunción Barbero、Pilar Castreño

  DOI：10.1002/ejoc.200901263

  日期：2010.3

  A new route for the synthesis of (epoxy-allyl)silanes bearing the PhMe 2 Si group has been developed and their acid-catalyzed cyclization studied. The so-called normal products derived from 5-exo or 6-endo attack were never obtained. On the contrary, an interesting tandem rearrangement/cyclization process was observed, which selectively led to 3-methylenecyclohexan-1-ols. A mechanism is proposed to

  已经开发了一种合成带有 PhMe 2 Si 基团的（环氧-烯丙基）硅烷的新途径，并研究了它们的酸催化环化。5-exo 或 6-endo 攻击衍生的所谓正常产物从未得到过。相反，观察到了一个有趣的串联重排/环化过程，它选择性地产生了 3-亚甲基环己-1-醇。提出了一种机制来解释这种串联反应。环化过程的立体选择性取决于催化剂的性质。
• From Silylated Trishomoallylic Alcohols to Dioxaspiroundecanes or Oxocanes: Catalyst and Substitution Influence
  作者：Asunción Barbero、Alberto Diez-Varga、Manuel Herrero、Francisco J. Pulido

  DOI：10.1021/acs.joc.5b02260

  日期：2016.4.1

  A versatile method for the synthesis of dioxaspiroundecanes through a tandem Sakurai–Prins cyclization of allylsilyl alcohols in the presence of TMSOTf is described. The process is general and highly stereoselective with total control in the creation of three new stereogenic centers in a single step. Moreover, a very interesting chemoselectivity has been observed depending on the nature of the catalyst

  描述了一种在TMSOTf存在下，通过串联Sakurai–Prins烯丙基硅醇的环化反应合成二恶灵螺烷的通用方法。该过程是通用的，具有高度的立体选择性，可在一个步骤中完全控制三个新的立体生成中心的创建。此外，根据所用催化剂的性质或三均烯丙基醇的取代，已观察到非常有趣的化学选择性，因为在BF 3 ·OEt 2催化下的相同反应或使用具有烯丙基取代基的醇通过直接甲硅烷基-Prins环化。
• Barbero, Asuncion; Pulido, Francisco J., Synthesis, 2004, # 5, p. 779 - 785
  作者：Barbero, Asuncion、Pulido, Francisco J.

  DOI：——

  日期：——
• Acid-Catalyzed Cyclization of Epoxyallylsilanes. An Unusual Rearrangement Cyclization Process
  作者：Asunción Barbero、Pilar Castreño、Francisco J. Pulido

  DOI：10.1021/ol035297v

  日期：2003.10.1

  synthesis of epoxyallylsilanes bearing the phenyldimethylsilyl group is reported that involves silylcupration of allene, conjugate addition to enones, and sulfur-ylide-mediated epoxidation. The Lewis acid-catalyzed cyclization of these substrates is presented. The expected normal products derived from 5-exo and/or 6-endo attack are not observed; instead, methylenecyclohexanols resulting from a tandem rea

  [反应：请参见文字]。据报道，合成带有苯基二甲基甲硅烷基的环氧烯丙基硅烷的新途径涉及甲硅烷基化丙二烯，将共轭物加成烯酮以及硫代叶立德介导的环氧化。呈现了路易斯酸催化的这些底物的环化。没有观察到源自5-exo和/或6-endo攻击的预期正常产物；而是形成了由串联重排-环化过程产生的亚甲基环己醇。
• Seven-Membered Ring Formation from Cyclopropanated Oxo- and Epoxyallylsilanes
  作者：Francisco J. Pulido、Asunción Barbero、Pilar Castreño

  DOI：10.1021/jo200705u

  日期：2011.7.15

  A useful strategy for cycloheptane annulations from oxo- and epoxyallylsilanes, prepared by silylcupration of allenes, has been developed, and their application to the stereoselective synthesis of 4-methylenecycloheptan-1-ols is of great potential in the construction of seven-membered ring natural products presented.