3-phenyl-1-trimethylsilyloxylcyclopent-1-ene | 69849-77-0

• 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-phenyl-1-trimethylsilyloxylcyclopent-1-ene
• 英文别名: 1-Trimethylsiloxy-3-phenylcyclopenten；trimethyl((3-phenylcyclopent-1-en-1-yl)oxy)silane；Trimethyl-(3-phenylcyclopenten-1-yl)oxysilane
• CAS: 69849-77-0
• 化学式: C₁₄H₂₀OSi
• 分子量: 232.398
• InChiKey: NSRQRACDABSDAC-UHFFFAOYSA-N

物化性质

• 沸点：
  276.6±40.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 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-phenyl-1-trimethylsilyloxylcyclopent-1-ene 在 甲基锂 、 phenyl copper 、 3-溴丙烯 作用下， 生成 3-苯基环戊酮
  参考文献：
  名称：

  A directing effect of neighboring aromatic groups on the regiochemistry of formation and stereochemistry of alkylation and bromination of ketone lithium enolates. Evidence for lithium-arene coordination and dramatic effect of copper(I) in controlling stereochemistry and limiting polyalkylation

  摘要：

  DOI：

  10.1021/ja00498a023
• 作为产物：
  描述：

  三甲基氯硅烷 、 2-环戊烯酮 、 phenylmagnesium bromide 在 copper(l) iodide 六甲基磷酰三胺 作用下， 以 四氢呋喃 为溶剂， 以94%的产率得到3-phenyl-1-trimethylsilyloxylcyclopent-1-ene
  参考文献：
  名称：

  A new 4-substituted-2-Cyclohexenone synthesis

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(00)79311-7

文献信息

• Alkynoate Synthesis through the Vinylogous Reactivity of Rhodium(II) Carbenoids
  作者：Damien Valette、Yajing Lian、John P. Haydek、Kenneth I. Hardcastle、Huw M. L. Davies

  DOI：10.1002/anie.201204047

  日期：2012.8.20

  Siloxy group migration: A rhodium(II) carbenoid approach has been developed for the synthesis of alkynoates (see scheme). This transformation combines the addition of enol ethers at the vinylogous position of β‐siloxy‐substituted vinyldiazo derivatives with a siloxy group migration to give the products as single diastereomers.

  甲硅烷氧基迁移：已经开发出铑(II)类胡萝卜素方法用于合成炔酸酯（参见方案）。这种转化将β-甲硅烷氧基取代的乙烯基重氮衍生物的插烯位置处的烯醇醚加成与甲硅烷氧基迁移结合起来，得到单一非对映体的产物。
• Mn(III)-Mediated Reactions of Cyclopropanols with Vinyl Azides: Synthesis of Pyridine and 2-Azabicyclo[3.3.1]non-2-en-1-ol Derivatives
  作者：Yi-Feng Wang、Shunsuke Chiba

  DOI：10.1021/ja905110c

  日期：2009.9.9

  to the formation of 2-azabicyclo[3.3.1]non-2-en-1-ol derivatives using a catalytic amount of Mn(acac)(3). These reactions may be initiated by a radical addition of beta-keto radicals, generated by the one-electron oxidation of cyclopropanols, to vinyl azides to give iminyl radicals, which would cyclize with the intramolecular carbonyl groups. In addition, versatile transformations of 2-azabicyclo[3.3

  Mn(III) 介导的取代吡啶和 2-氮杂双环 [3.3.1] 非 2-en-1-ol 衍生物的发散合成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进行开发。简而言之，在 Mn(acac)(3)（1.7 当量）存在下，乙烯基叠氮化物与单环环丙醇反应生成吡啶，而与双环环丙醇反应生成 2-氮杂双环 [3.3.1]non-2 -en-1-ol 衍生物，使用催化量的 Mn(acac)(3)。这些反应可以通过将环丙醇单电子氧化产生的β-酮基自由基加成到乙烯基叠氮化物以产生亚胺基自由基来引发，亚胺基自由基会与分子内羰基环化。此外，2-氮杂双环[3.3.1]non-2-en-1-ol 到 2-氮杂双环[3.3] 的通用转化。
• Soft Enolization of 3-Substituted Cycloalkanones Exhibits Significantly Improved Regiocontrol vs Hard Enolization Conditions
  作者：Natalie C. Dwulet、Vincenzo Ramella、Christopher D. Vanderwal

  DOI：10.1021/acs.orglett.1c03844

  日期：2021.12.17

  markedly better than the typically applied hard enolization protocols for regioselective enoxysilane formation from unsymmetrical 3-substituted cycloalkanones. Five-, six-, and seven-membered cycloalkanones each with 3-methyl, 3-isopropyl, or 3-phenyl substituents were investigated, and in all but one case, regioselectivities were ≥11:1 for enolization away from the substituent. These results are complementary

  研究表明，从不对称 3-取代环烷酮形成区域选择性烯氧基硅烷时，软烯醇化条件明显优于通常应用的硬烯醇化方案。研究了各自带有 3-甲基、3-异丙基或 3-苯基取代基的五元、六元和七元环烷酮，除了一种情况外，在所有情况下，远离取代基的烯醇化的区域选择性≥11:1。这些结果与由环烯酮缀合物加成/烯醇化物硅烷化衍生的区域特异性烯氧基硅烷形成是互补的。
• Iron(III) mediated transformations of trimethylsilyloxy cyclopropyl ethers
  作者：Kevin I. Booker-Milburn、David F. Thompson

  DOI：10.1016/0040-4020(95)00817-r

  日期：1995.11

  Conjugate addition of a variety of Grignard reagents to 2-cyclopentenone gave a number of silyl enol ethers (1) which were Created with Et2Zn/CH2I2 to give the corresponding cyclopropyl silyl ethers (2) in good yield. Ferric chloride ring expansion followed by base elimination of the resulting β-chloro ketones gave the 4-substituted-2-cyclohexenones (4) in moderate to good overall yield. The overall

  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。
• Trimethylsilyl chloride/tetramethylethylenediamine facilitated additions of organocopper reagents (RCu) to enones
  作者：Carl R. Johnson、Thomas J. Marren

  DOI：10.1016/s0040-4039(00)95640-5

  日期：1987.1