3-(2-hydroxyethoxy)-3-methyl-5-(diphenylmethylsilyl)-2-(2-phenylethyl)cyclopentanone | 147914-09-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(2-hydroxyethoxy)-3-methyl-5-(diphenylmethylsilyl)-2-(2-phenylethyl)cyclopentanone
• 英文别名: 3-(2-Hydroxyethoxy)-3-methyl-5-[methyl(diphenyl)silyl]-2-(2-phenylethyl)cyclopentan-1-one
• CAS: 147914-09-8
• 化学式: C₂₉H₃₄O₃Si
• 分子量: 458.673
• InChiKey: FVWNZTGILVIJDV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.24
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 3-(2-hydroxyethoxy)-3-methyl-5-(diphenylmethylsilyl)-2-(2-phenylethyl)cyclopentanone 在 sodium hydride 作用下， 生成 3-methyl-5-methylene-2-(2-phenylethyl)-2-cyclopenten-1-one
  参考文献：
  名称：

  Highly substituted .alpha.-silylated cyclopentanones from ethyl levulinate: an entry to a methylenomycin B analog

  摘要：

  The transformation of alpha-diphenylmethylsilylated ethyl levulinate acetal, 1, to a series of alpha-silylated cyclopentanones has been studied. The approach was based on a three-step process in which 1 was initially transformed into alpha-(diphenylmethylsilyl)-gamma-(ethylenedioxy) ketones by its reaction with Grignard reagents. A novel highly substituted 2,3-dihydrofuran was also obtained as a secondary product. Deprotonation-trimethylsilylation of these ketones under kinetic conditions produced 3-silylated-2-silyl enol ethers in a regio- and stereoselective manner. The Z isomer was shown to predominate. These enol ethers were stereoselectively transformed into alpha-silylated cyclopentanones by a TiCl4-promoted intramolecular Mukaiyama reaction. The geometry of the silyl enol ethers determined the stereochemistry of the cyclic ketone products, and the integrity of the diphenylmethylsilyl group was maintained. A methylenomycin B analog was prepared in one pot from one of the polyfunctional ketones by means of a beta-alkoxy elimination followed by a Peterson-type alpha-methylenation with formaldehyde. This analog, 3-methyl-5-methylene-2-(2-phenylethyl)-2-cyclopenten-1-one, 12, showed in vitro cytotoxicity against CHO-K1 cells.

  DOI：

  10.1021/jo00062a012
• 作为产物：
  描述：

  3-phenylpropyl-magnesium bromide 在 四氯化钛 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 77.75h， 生成 3-(2-hydroxyethoxy)-3-methyl-5-(diphenylmethylsilyl)-2-(2-phenylethyl)cyclopentanone
  参考文献：
  名称：

  Highly substituted .alpha.-silylated cyclopentanones from ethyl levulinate: an entry to a methylenomycin B analog

  摘要：

  The transformation of alpha-diphenylmethylsilylated ethyl levulinate acetal, 1, to a series of alpha-silylated cyclopentanones has been studied. The approach was based on a three-step process in which 1 was initially transformed into alpha-(diphenylmethylsilyl)-gamma-(ethylenedioxy) ketones by its reaction with Grignard reagents. A novel highly substituted 2,3-dihydrofuran was also obtained as a secondary product. Deprotonation-trimethylsilylation of these ketones under kinetic conditions produced 3-silylated-2-silyl enol ethers in a regio- and stereoselective manner. The Z isomer was shown to predominate. These enol ethers were stereoselectively transformed into alpha-silylated cyclopentanones by a TiCl4-promoted intramolecular Mukaiyama reaction. The geometry of the silyl enol ethers determined the stereochemistry of the cyclic ketone products, and the integrity of the diphenylmethylsilyl group was maintained. A methylenomycin B analog was prepared in one pot from one of the polyfunctional ketones by means of a beta-alkoxy elimination followed by a Peterson-type alpha-methylenation with formaldehyde. This analog, 3-methyl-5-methylene-2-(2-phenylethyl)-2-cyclopenten-1-one, 12, showed in vitro cytotoxicity against CHO-K1 cells.

  DOI：

  10.1021/jo00062a012