(1R,4R,5S,6S)-6-hydroxy-5-phenylbicyclo[2.2.2]octan-2-one | 1131282-53-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,4R,5S,6S)-6-hydroxy-5-phenylbicyclo[2.2.2]octan-2-one
• CAS: 1131282-53-5
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: VBYAEPOBIZACRL-ZMJPVWNMSA-N

物化性质

• 沸点：
  384.0±42.0 °C(Predicted)
• 密度：
  1?+-.0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,4R,5S,6S)-6-hydroxy-5-phenylbicyclo[2.2.2]octan-2-one 在 2,4,6-三甲基吡啶 、 甲基磺酰氯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 2-(4-phenoxyphenyl)-5-phenylbicyclo[2.2.2]octa-2,5-diene
  参考文献：
  名称：

  Scalable Synthesis of Enantiomerically Pure Bicyclo[2.2.2]octadiene Ligands

  摘要：

  An operationally simple and scalable synthesis of enantiomerically pure bicyclo[2.2.2]octadiene (bod*) ligands relying on an organocatalytic one-pot Michael addition-aldol reaction with cheap 2-cyclohexenone and phenylacetaldehyde is presented. The crystalline bicyclic product 4a (6-hydroxy-5-phenylbicyclo[2.2.2]octan-2-one) is transformed into phenylbicyclo[2.2.2]oct-5-en-2-one 2, a versatile starting material for the 2-step synthesis of both symmetrical, such as Hayashi's Ph-bod* ligand, as well as novel unsymmetrical chiral dienes.

  DOI：

  10.1021/jo3005638
• 作为产物：
  描述：

  2-(3-oxocyclohexyl)-2-phenylacetaldehyde 生成 (1R,4R,5S,6S)-6-hydroxy-5-phenylbicyclo[2.2.2]octan-2-one
  参考文献：
  名称：

  设计和放大实用的对映选择性路线到5-苯基双环[2.2.2] oct-5-en-2-one

  摘要：

  设计并开发了一种实用的手性5-苯基双环[2.2.2] oct-5-en-2-one 1的对映体选择性路线。从2-环己烯酮以22％的产率获得了无色晶体的目标化合物，其对映体比率高于99.5：0.5，并且化学纯度特别高（> 99％）。分离出九个化学步骤中的三个中间体。值得注意的是，尽管除一种中间体以外的所有中间体都是油，但该方法没有任何色谱法或蒸馏法。成功的关键是优化原位制备的酮醛的分子内羟醛反应，生成固体中间体（1 R，4 R，4 S，6 S）-6-羟基双环[2.2.2] octan-2-one 9a分离出来的化学和手性纯度很高。这是分子内结晶诱导的非对映异构体转化（CIDT）的一个例子。该仲醇的脱水至1需要对反应条件进行广泛的筛选，以确保优异的纯度，这对于该低熔点化合物的结晶是必不可少的。最终过程既简单又浓缩，正如在30 L的反应器中在10个工作日内快速合成1千克1所证明的那样。

  DOI：

  10.1021/op200305y

文献信息

• PREPARATION OF BICYCLO[2.2.2]OCTAN-2-ONE COMPOUNDS
  申请人：Abele Stefan

  公开号：US20130211104A1

  公开（公告）日：2013-08-15

  The present invention relates to a new process for the preparation of 6-hydroxy-5-arylbicyclo[2.2.2]octan-2-one compounds of the formula (II); which may subsequently be further transformed to compounds of the formula (I): The present invention further relates to novel compounds as such, which compounds are useful intermediates in the above process.

  本发明涉及一种制备公式（II）的6-羟基-5-芳基双环[2.2.2]辛烷-2-酮化合物的新工艺，该化合物随后可进一步转化为公式（I）的化合物： 本发明还涉及上述过程中有用的新化合物作为中间体。
• [EN] DIASTEREOSELECTIVE PREPARATION OF BICYCLO[2.2.2]OCTAN-2-ONE COMPOUNDS<br/>[FR] PRÉPARATION DIASTÉRÉOSÉLECTIVE DE COMPOSÉS BICYCLO[2.2.2]OCTAN-2-ONES
  申请人：ACTELION PHARMACEUTICALS LTD

  公开号：WO2012052943A1

  公开（公告）日：2012-04-26

  The present invention relates to a new process for the diastereoselective preparation of (1R*,4R*,5S*,6S*)-6-hydroxy-5-arylbicyclo[2.2.2]octan-2-one compounds, the compounds of the formula (II), which may subsequently be further transformed to 5-aryl-bicyclo[2.2.2]oct-5-en-2-one compounds of the formula (I): Formula (I), Formula (II). The present invention further relates to novel (1R*,2S*,3S*,4R*)-6-oxo-3-arylbicyclo[2.2.2]octan-2-yl methanesulfonate compounds as such, which compounds are useful intermediates in the preparation of 5-aryl-bicyclo[2.2.2]oct-5-en-2-one compounds of the formula (I).

  本发明涉及一种新的过程，用于对(1R*，4R*，5S*，6S*)-6-羟基-5-芳基双环[2.2.2]辛烷-2-酮化合物进行对映选择性制备，该化合物为公式(II)的化合物，该化合物随后可以进一步转化为公式(I)的5-芳基双环[2.2.2]辛-5-烯-2-酮化合物。本发明还涉及新的(1R*，2S*，3S*，4R*)-6-氧代-3-芳基双环[2.2.2]辛烷-2-甲磺酸酯化合物，这些化合物本身就是有用的中间体，用于制备公式(I)的5-芳基双环[2.2.2]辛-5-烯-2-酮化合物。
• DIASTEREOSELECTIVE PREPARATION OF BICYCLO[2.2.2]OCTAN-2-ONE COMPOUNDS
  申请人：Abele Stefan

  公开号：US20130289295A1

  公开（公告）日：2013-10-31

  The present invention relates to a new process for the diastereoselective preparation of (1R*,4R*,5S*,6S*)-6-hydroxy-5-arylbicyclo[2.2.2]octan-2-one compounds, the compounds of the formula (II), which may subsequently be further transformed to 5-aryl-bicyclo[2.2.2]oct-5-en-2-one compounds of the formula (I): The present invention further relates to novel (1R*,2S*,3S*,4R*)-6-oxo-3-arylbicyclo[2.2.2]octan-2-yl methanesulfonate compounds as such, which compounds are useful intermediates in the preparation of 5-aryl-bicyclo[2.2.2]oct-5-en-2-one compounds of the formula (I).

  本发明涉及一种新的过程，用于选择性地制备(1R*，4R*，5S*，6S*)-6-羟基-5-芳基双环[2.2.2]辛-2-酮化合物，即式(II)的化合物，该化合物随后可以进一步转化为式(I)的5-芳基双环[2.2.2]辛-5-烯-2-酮化合物：本发明还涉及新型(1R*，2S*，3S*，4R*)-6-氧代-3-芳基双环[2.2.2]辛-2-基甲磺酸酯化合物，这些化合物本身就是有用的中间体，用于制备式(I)的5-芳基双环[2.2.2]辛-5-烯-2-酮化合物。
• Hydrazone-Initiated Carbene/Alkyne Cascades to Form Polycyclic Products: Ring-Fused Cyclopropenes as Mechanistic Intermediates
  作者：Phong Q. Le、Jeremy A. May

  DOI：10.1021/jacs.5b08157

  日期：2015.9.30

  A hydrazone-based carbene/alkyne cascade produced a variety of bridged and fused polycyclic products. NaOSiMe3 is a superior base for conversion of hydrazones to diazoalkanes. A key mechanistic intermediate, a ring-fused cyclopropene, has been isolated and characterized.
• US8816118B2
  申请人：——

  公开号：US8816118B2

  公开（公告）日：2014-08-26