(S)-5-(dimethyl(phenyl)silyl)cyclohex-2-enone | 244109-45-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-5-(dimethyl(phenyl)silyl)cyclohex-2-enone
• 英文别名: (5S)-5-[dimethyl(phenyl)silyl]cyclohex-2-en-1-one
• CAS: 244109-45-3
• 化学式: C₁₄H₁₈OSi
• 分子量: 230.382
• InChiKey: NEGUCCJYLKIZCL-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.89
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-5-(dimethyl(phenyl)silyl)cyclohex-2-enone 、 4,6-dimethoxy-3-oxo-1,3-dihydroisobenzofuran-1-carbonitrile 在 lithium bis[trimethylsilyl]amide 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以65%的产率得到(S)-3-(dimethyl(phenyl)silyl)-9,10-dihydroxy-6,8-dimethoxy-3,4-dihydroanthracen-1(2H)-one
  参考文献：
  名称：

  Total Syntheses of 2,2‘-epi-Cytoskyrin A, Rugulosin, and the Alleged Structure of Rugulin

  摘要：

  The total syntheses of 2,2'-epi-cytoskyrin A, rugulosin, and the alleged structure of rugulin are described. These naturally occurring bisanthraquinones and their relatives are characterized by novel molecular architectures at the core, at which lies a more or less complete, cage-like structural motif termed "skyrane". The strategies developed for their total synthesis feature a cascade sequence called the "cytoskyrin cascade" and deliver these molecules in short order and in a stereoselective manner.

  DOI：

  10.1021/ja0685708
• 作为产物：
  描述：

  3-(dimethyl(phenyl)silyl)cyclohexanone 在 palladium diacetate 重铬酸吡啶 、 Amano Lipase PS 、 4 A molecular sieve 、 氧气 、 sodium methylate 、 lithium tri-t-butoxyaluminum hydride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 异丙醚 、 二甲基亚砜 为溶剂， -78.0~23.0 ℃ 、133.32 Pa 条件下， 反应 79.0h， 生成 (S)-5-(dimethyl(phenyl)silyl)cyclohex-2-enone
  参考文献：
  名称：

  对映体纯的5-（三烷基甲硅烷基）-2-环己烯酮的简单实用方法。

  摘要：

  [反应：见正文]对映体纯的手性5-甲硅烷基化的2-环己烯酮很容易以高收率制备，其关键步骤是用市售脂肪酶进行动力学拆分。完全活性的酶可以非常有效地回收再利用。方案1和方案3概述了合成步骤。对映体纯的2-环己酮如1和2是通过各种非对映选择性反应如方案2所示的合成多种手性靶的通用中间体。

  DOI：

  10.1021/ol990805f

文献信息

• Organocatalytic Asymmetric Synthesis of 5-(Trialkylsilyl)cyclohex-2-enones and the Transformation into Useful Building Blocks
  作者：Patrick Bolze、Gustav Dickmeiss、Karl Anker Jørgensen

  DOI：10.1021/ol801392d

  日期：2008.9.1

  A simple organocatalytic approach to highly attractive chiral building blocks is presented. By the reaction of beta-ketoesters with alpha,beta-unsaturated aldehydes using a chiral TINS-protected prolinol as the catalyst, optically active 5-(trialkylsilyl)cyclohex-2-enones are formed in good yields and with 98-99% ee. The applications of 5-(trialkylsilyl)cyclohex-2-enones for the formation of 5-(hydroxy)cyclohex-2-enones and the A-ring of 19-nor-1 alpha,25-dihydroxyvitamin D-3 are also presented.
• Total Syntheses of 2,2‘-<i>epi</i>-Cytoskyrin A, Rugulosin, and the Alleged Structure of Rugulin
  作者：K. C. Nicolaou、Yee Hwee Lim、Jared L. Piper、Charles D. Papageorgiou

  DOI：10.1021/ja0685708

  日期：2007.4.1

  The total syntheses of 2,2'-epi-cytoskyrin A, rugulosin, and the alleged structure of rugulin are described. These naturally occurring bisanthraquinones and their relatives are characterized by novel molecular architectures at the core, at which lies a more or less complete, cage-like structural motif termed "skyrane". The strategies developed for their total synthesis feature a cascade sequence called the "cytoskyrin cascade" and deliver these molecules in short order and in a stereoselective manner.
• Simple and Practical Routes to Enantiomerically Pure 5-(Trialkylsilyl)-2-cyclohexenones
  作者：Georgios Sarakinos、E. J. Corey

  DOI：10.1021/ol990805f

  日期：1999.9.1

  [reaction: see text] Enantiomerically pure chiral 5-silylated 2-cyclohexenones are easily prepared in high yield using as a key step kinetic resolution with a commercially available lipase. Fully active enzyme can be recovered very efficiently for reuse. The synthetic steps are outlined in Schemes 1 and 3. Enantiomerically pure 2-cyclohexenones such as 1 and 2 are versatile intermediates for the synthesis

  [反应：见正文]对映体纯的手性5-甲硅烷基化的2-环己烯酮很容易以高收率制备，其关键步骤是用市售脂肪酶进行动力学拆分。完全活性的酶可以非常有效地回收再利用。方案1和方案3概述了合成步骤。对映体纯的2-环己酮如1和2是通过各种非对映选择性反应如方案2所示的合成多种手性靶的通用中间体。