(S)-trimethyl((3-methyl-3-(4-methyl-3-(prop-1-en-2-yl)pent-3-en-1-yl)cyclohex-1-en-1-yl)oxy)silane | 1350704-15-2

• 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: (S)-trimethyl((3-methyl-3-(4-methyl-3-(prop-1-en-2-yl)pent-3-en-1-yl)cyclohex-1-en-1-yl)oxy)silane
• 英文别名: (S)-Trimethyl{{3-methyl-3-[4-methyl-3-(prop-1-en-2-yl)pent-3-en-1-yl]cyclohex-1-en-1-yl}oxy}silane；trimethyl-[(3S)-3-methyl-3-(4-methyl-3-prop-1-en-2-ylpent-3-enyl)cyclohexen-1-yl]oxysilane
• CAS: 1350704-15-2
• 化学式: C₁₉H₃₄OSi
• 分子量: 306.564
• InChiKey: ATKFKZVXAWMIOD-IBGZPJMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 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：

  (S)-trimethyl((3-methyl-3-(4-methyl-3-(prop-1-en-2-yl)pent-3-en-1-yl)cyclohex-1-en-1-yl)oxy)silane 在 Jones reagent 、 gadolinium(III) trifluoromethanesulfonate 作用下， 以 丙酮 、 甲苯 为溶剂， 反应 120.0h， 生成 (2R,3S)-2-acryloyl-3-methyl-3-(4-methyl-3-(prop-1-en-2-yl)pent-3-en-1-yl)cyclohexanone
  参考文献：
  名称：

  Route Optimization and Synthesis of Taxadienone

  摘要：

  Early process development toward the scalable production of taxadienone on a decagram scale is described. A continuous flow reactor was employed to safely run a potentially hazardous cyclopropane ring opening. The route featured two copper-mediated additions, a Diels-Alder reaction and a palladium-catalyzed Negishi coupling, to construct the final structure.

  DOI：

  10.1021/op500314c
• 作为产物：
  描述：

  2,2,3,3-tetramethyl-1,1-dibromocyclopropane 在 噻吩-2-甲酸亚铜(I) 、 (R,R)-(PhMeCH)2N-P(-2-O-3,5-diMe-C₆H₂-C₆H₂-3',5'-diMe-2'-O-) 、 仲丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 环己烷 、 N,N-二甲基苯胺 为溶剂， 反应 5.74h， 生成 (S)-trimethyl((3-methyl-3-(4-methyl-3-(prop-1-en-2-yl)pent-3-en-1-yl)cyclohex-1-en-1-yl)oxy)silane
  参考文献：
  名称：

  Route Optimization and Synthesis of Taxadienone

  摘要：

  Early process development toward the scalable production of taxadienone on a decagram scale is described. A continuous flow reactor was employed to safely run a potentially hazardous cyclopropane ring opening. The route featured two copper-mediated additions, a Diels-Alder reaction and a palladium-catalyzed Negishi coupling, to construct the final structure.

  DOI：

  10.1021/op500314c

文献信息

• Scalable enantioselective total synthesis of taxanes
  作者：Abraham Mendoza、Yoshihiro Ishihara、Phil S. Baran

  DOI：10.1038/nchem.1196

  日期：2012.1

  Taxanes form a large family of terpenes comprising over 350 members, the most famous of which is Taxol (paclitaxel), a billion-dollar anticancer drug. Here, we describe the first practical and scalable synthetic entry to these natural products via a concise preparation of (+)-taxa-4(5),11(12)-dien-2-one, which has a suitable functional handle with which to access more oxidized members of its family. This route enables a gram-scale preparation of the ‘parent’ taxane—taxadiene—which is the largest quantity of this naturally occurring terpene ever isolated or prepared in pure form. The characteristic 6-8-6 tricyclic system of the taxane family, containing a bridgehead alkene, is forged via a vicinal difunctionalization/Diels–Alder strategy. Asymmetry is introduced by means of an enantioselective conjugate addition that forms an all-carbon quaternary centre, from which all other stereocentres are fixed through substrate control. This study lays a critical foundation for a planned access to minimally oxidized taxane analogues and a scalable laboratory preparation of Taxol itself. The taxane diterpene family is structurally complex and exhibits a wide range of biological activities, best exemplified by the successful drug Taxol. Here, two of the least oxidized taxanes in the family, ‘taxadienone’ and taxadiene, are prepared by total synthesis on a gram scale. The concise synthetic route described herein provides a scalable, enantioselective entry to the taxane family of natural products.

  紫杉类化合物是一个庞大的萜类化合物家族，由 350 多个成员组成，其中最著名的是 Taxol（紫杉醇），这是一种价值数十亿美元的抗癌药物。在这里，我们描述了通过简易制备 (+)-taxa-4(5),11(12)-dien-2-one 首次进入这些天然产品的实用和可扩展的合成途径。通过这一途径，我们以克为单位制备出了 "母体 "紫杉烷-紫杉二烯，这是迄今为止分离或制备纯度最高的天然萜烯。紫杉烷家族特有的 6-8-6 三环体系包含一个桥头烯，是通过邻位二官能化/DielsâAlder 方法形成的。通过对映选择性共轭加成法引入了不对称，形成了一个全碳四元中心，通过底物控制固定了所有其他立体中心。这项研究为计划获得氧化程度极低的紫杉烷类似物和实验室制备紫杉醇本身奠定了重要基础。紫杉烷二萜家族结构复杂，具有广泛的生物活性，成功的药物紫杉醇就是最好的例子。本文以克为单位，通过全合成法制备了该家族中氧化程度最低的两种紫杉烷，即紫杉二烯酮（§taxadienoneâ）和紫杉二烯（§taxadiene）。本文描述的简明合成路线提供了一种可扩展的、对映选择性的天然紫杉烷家族产品。