3-allyl-1-trimethylsilyloxylcyclopent-1-ene | 153788-35-3

• 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: 3-allyl-1-trimethylsilyloxylcyclopent-1-ene
• 英文别名: (3-allylcyclopent-1-enyloxy)trimethylsilane；Trimethyl-(3-prop-2-enylcyclopenten-1-yl)oxysilane
• CAS: 153788-35-3
• 化学式: C₁₁H₂₀OSi
• 分子量: 196.365
• InChiKey: BEJITZQGVQQTLQ-UHFFFAOYSA-N

物化性质

• 沸点：
  204.2±19.0 °C(Predicted)
• 密度：
  0.88±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.71
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-allyl-1-trimethylsilyloxylcyclopent-1-ene 在 diethylzinc 、 sodium acetate 、 三氯化铁 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 6.0h， 生成 4-(2-丙烯基)-2-环己烯-1-酮
  参考文献：
  名称：

  铁（III）介导的三甲基甲硅烷氧基环丙基醚的转化：第2部分：一种新的4-取代的-2-环己烯酮合成

  摘要：

  在2-环戊烯酮中共轭添加各种格氏试剂，得到了许多甲硅烷基烯醇醚（1），它们由Et 2 Zn / CH 2 I 2生成，以高收率得到了相应的环丙基甲硅烷基醚（2）。氯化铁环膨胀，然后碱消除所得的β-氯代酮，以中等至良好的总收率得到4-取代的2-环己烯酮（4）。整个过程提供了从2-环戊烯酮到这些烯酮的方便的三步路线。

  DOI：

  10.1016/0040-4020(95)00817-r
• 作为产物：
  描述：

  2-环戊烯酮 、 烯丙基三甲基硅烷 在 copper(l) chloride 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以61%的产率得到3-allyl-1-trimethylsilyloxylcyclopent-1-ene
  参考文献：
  名称：

  Michael reactions of silylated nucleophiles with conjugated enones accompanied by silyl group transfer catalysed by copper(I) chloride under photoirradiation

  摘要：

  共轭烯酮与硅烷化亲核试剂如硅缩醛、烯醇硅醚甚至烯丙基硅烷的光反应，导致了硅基转移伴随的迈克尔加成物的形成。

  DOI：

  10.1039/c39940001759

文献信息

• Studies towards the Synthesis of Pentalenene: Mechanistic Insights into the Isomerization Phenomenon During RCM of Medium-Sized Rings
  作者：Guillaume De Bo、István E. Markó

  DOI：10.1002/ejoc.201001475

  日期：2011.4

  Isomerization issues have been encountered during the ring-closing metathesis (RCM) step of a new approach towards pentalenene. This paper describes the mechanistic insights gained during the study of this side reaction from a substrate perspective. Isomerization issues have been encountered during the RCM step of a new approach towards pentalenene.

  在戊烯新方法的闭环复分解 (RCM) 步骤中遇到了异构化问题。本文从底物的角度描述了在研究这种副反应期间获得的机理见解。在对戊烯的新方法的 RCM 步骤中遇到了异构化问题。
• Studies towards the total synthesis of an epoxy isoprostane phospholipid, a potent activator of endothelial cells
  作者：Michael E. Jung、Annika Kers、Ganesamoorthy Subbanagounder、Judith A. Berliner

  DOI：10.1039/b209892j

  日期：2003.1.7

  We report studies toward the total synthesis of an epoxy isoprostane, namely the preparation of compound 9 which is an analogue of the elimination product 7 of the naturally occurring epoxy isoprostane 4 by a straightforward route using a three-component coupling, and have shown by several spectroscopic criteria that it closely resembles the natural material.

  我们报道了有关于环氧异前列腺素的总合成研究，即通过简单的三组分偶联法制备化合物9，该化合物是天然存在的环氧异前列腺素4的消除产物7的类比物，并通过几种光谱标准显示其与天然物质非常相似。
• Mn(III)-Mediated Formal [3+3]-Annulation of Vinyl Azides and Cyclopropanols: A Divergent Synthesis of Azaheterocycles
  作者：Yi-Feng Wang、Kah Kah Toh、Eileen Pei Jian Ng、Shunsuke Chiba

  DOI：10.1021/ja200879w

  日期：2011.4.27

  Mn(III)-mediated formal [3+3]-annulation has been developed using readily available vinyl azides and cyclopropanols with a wide range of substituents. Vinyl azides were successfully applied as a three-atom unit including one nitrogen to prepare pyridines and δ-lactams by the reactions with monocyclic cyclopropanols as well as to construct 2-azabicyclo[3.3.1] and 2-azabicyclo[4.3.1] frameworks with

  Mn(III) 介导的正式[3+3]-环化已经使用容易获得的乙烯基叠氮化物和具有广泛取代基的环丙醇开发。乙烯基叠氮化物作为一个含一个氮的三原子单元，通过与单环环丙醇反应制备吡啶和δ-内酰胺，以及构建2-氮杂双环[3.3.1]和2-氮杂双环[4.3.1]骨架，成功应用与双环环丙醇、双环[3.1.0]己-1-醇和双环[4.1.0]庚-1-醇。这些反应是通过 β-羰基自由基的自由基加成引发的，β-羰基自由基是由环丙醇与 Mn(III) 的单电子氧化产生的，与乙烯基叠氮化物产生亚胺基自由基，亚胺基自由基与分子内的羰基环化。此外，将本方法应用于合成四元吲哚生物碱，melinonine-E，
• Conjugate Addition Reactions of Allylic Copper Species Derived from Grignard Reagents: Synthetic and Spectroscopic Aspects
  作者：Bruce H. Lipshutz、Claus Hackmann

  DOI：10.1021/jo00103a042

  日期：1994.12

  A general study on the 1,4-addition chemistry of allyl, methallyl, crotyl, and prenyl Grignard-derived organocopper reagents has been conducted. While diallylic cuprates formed from such species are not effective Michael donors, the 1:1:1 combination of an allylic Grignard, CuBr.SMe(2), and Me(3)SiCl leads to high yields of 1,4-adducts. The stereo- and regiochemistry associated with the allylic ligand, where appropriate, has also been examined. Low temperature C-13 NMR studies provide insight as to the nature of these complexes.
• A new 4-substituted-2-Cyclohexenone synthesis
  作者：Kevin I. Booker-Milburn、David F. Thompson

  DOI：10.1016/s0040-4039(00)79311-7

  日期：1993.11

  Conjugate addition of a variety of Grignard reagents to 2-cyclopentenone followed by cyclopropanation of the resulting enol ethers gave a range of substituted cyclopropyl silyl ethers in good yield. Treatment of these cyclopropyl silyl ethers with ferric chloride in DMF gave the one carbon ring expanded beta-chloro ketones which were eliminated to the corresponding 4- substituted-2-cyclohexenones.