1-(1-undecyloxy-propa-1,2-dienyl)-cyclobutanol | 890903-48-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(1-undecyloxy-propa-1,2-dienyl)-cyclobutanol
• CAS: 890903-48-7
• 化学式: C₁₈H₃₂O₂
• 分子量: 280.451
• InChiKey: OKUMHVZAVMMFSY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  20
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(1-undecyloxy-propa-1,2-dienyl)-cyclobutanol 在 (dibenzylideneacetone)3palladium⁽⁰⁾ monochloroform complex 、 (R,R)-stilbene ligand 4 A molecular sieve 、 三乙胺 、 苯甲酸 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 12.0h， 生成 2-undecyloxy-2-vinylcyclopentanone 、 2-undecyloxy-2-vinylcyclopentanone
  参考文献：
  名称：

  Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event

  摘要：

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.

  DOI：

  10.1021/ja7111299
• 作为产物：
  描述：

  1-prop-2-ynyloxy-undecane 在 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.0h， 生成 1-(1-undecyloxy-propa-1,2-dienyl)-cyclobutanol
  参考文献：
  名称：

  钯催化的烯基环丁醇的不对称扩环：不对称 Wagner-Meerwein Shift

  摘要：

  在这项研究中，我们开发了钯催化的烯基环丁醇底物的原子经济不对称 Wagner-Meerwein 位移。它是通过烯基环丁醇的扩环来产生具有α-手性O-叔中心的官能化环戊酮的极好方法。该反应由氢化钯反应引发，并提供优异的对映选择性和原子经济性。该方法提供了合成天然产物的有效途径，例如 trans-kumausyne 家族、螺环系统。此外，我们通过使用 3-单取代的烯丙基环丁醇同时获得了优异的非对映选择性和对映选择性。

  DOI：

  10.1021/ja0602501

文献信息

• Palladium-Catalyzed Asymmetric Ring Expansion of Allenylcyclobutanols:  An Asymmetric Wagner−Meerwein Shift
  作者：Barry M. Trost、Jia Xie

  DOI：10.1021/ja0602501

  日期：2006.5.1

  In this study, we developed a palladium-catalyzed atom economic asymmetric Wagner-Meerwein shift of allenylcyclobutanol substrates. It is an excellent method for creating functionalized cyclopentanones with an alpha-chiral O-tertiary center by ring expansion of allenylcyclobutanols. This reaction was initiated by hydropalladation and afforded excellent enantioselectivity as well as atom economy. This

  在这项研究中，我们开发了钯催化的烯基环丁醇底物的原子经济不对称 Wagner-Meerwein 位移。它是通过烯基环丁醇的扩环来产生具有α-手性O-叔中心的官能化环戊酮的极好方法。该反应由氢化钯反应引发，并提供优异的对映选择性和原子经济性。该方法提供了合成天然产物的有效途径，例如 trans-kumausyne 家族、螺环系统。此外，我们通过使用 3-单取代的烯丙基环丁醇同时获得了优异的非对映选择性和对映选择性。
• Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event
  作者：Barry M. Trost、Jia Xie

  DOI：10.1021/ja7111299

  日期：2008.5.1

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.