3-(6-oxocyclohex-1-en-1-yl)propanal | 196790-61-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(6-oxocyclohex-1-en-1-yl)propanal
• 英文别名: 3-(6-Oxocyclohexen-1-yl)propanal
• CAS: 196790-61-1
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: DKUGAQZAJRIDNN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(6-oxocyclohex-1-en-1-yl)propanal 在 4-二甲氨基吡啶 、 三氟乙酸 、 三氯氧磷 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 生成 tert-butyl (4aRS,12bRS,14aRS)-1-chloro-2-formyl-4,4a,6,7,12b,13,14,14a-octahydroindolo[2',3':3,4]pyrido[1,2-a]quinoline-12(3H)-carboxylate
  参考文献：
  名称：

  橘皮碱的合成

  摘要：

  外消旋形式的Tangutorine（1）由色胺和醛3组装而成。合成设计基于在甲酮2的非色胺部分中发现隐藏的对称性。用7％的总产率甲五个步骤中开发了其中2转化成目标分子通过一个维尔斯迈尔-哈克反应和两个还原步骤。

  DOI：

  10.1002/hlca.200690003
• 作为产物：
  描述：

  2-Ethoxy-2,3,4,6,7,8-hexahydro-chromen-5-one 在 盐酸 、 lithium aluminium tetrahydride 作用下， 以 水 、 丙酮 为溶剂， 反应 1.5h， 生成 3-(6-oxocyclohex-1-en-1-yl)propanal
  参考文献：
  名称：

  Designing Photosystems for Harvesting Photons into Electrons by Sequential Electron-Transfer Processes:  Reversing the Reactivity Profiles of α,β-Unsaturated Ketones as Carbon Radical Precursor by One Electron Reductive β-Activation

  摘要：

  Two photosystems are developed to harvest visible-light photons into electrons via sequential electron transfer processes. Photosystem-A (PS-A) consisted of DCA as light harvesting electron acceptor and Ph3P as sacrificial electron donor, whereas photosystem-B (PS-B) employed DCA as usual electron acceptor, DMN as a primary electron donor, and ascorbic acid as a secondary and sacrificial election donor. alpha,beta-Unsaturated ketones are utilized as secondary electron acceptors. The design of these photosystems is based on the thermodynamic feasibility of electron transfer between each participating components. Electron transfer from DCA(.-) to alpha,beta-unsaturated ketones leads to their beta-activation as carbon centered radicals which cyclizes efficiently to tethered activated olefins. Cyclization with a nonactivated olefin is found to be moderate. The cyclization stereochemistries have been illustrated by studying the PET activation of 5 and 21. The exclusive trans-stereochemistry observed in 8 is explained by considering the thermodynamic, equilibration of initially formed syn-intermediate 10 from 5. The isolation of trace amount of 9 in this reaction substantiates the syn-intermediacy as primary intermediate which is further confirmed by the isolation of 25 from 21. Formation of 25 suggests that wherever the syn-intermediate is thermodynamically more stable, it invariably undergoes further cyclization to geometrically well-placed enolate double bond. An interesting observation is made by isolating 9 as a major product from the PET activation of 5 using PS-B. Stabilization of 10 by ascorbic acid is suggested to be the plausible explanation for this unusual observation. Radicals produced by the reductive beta-activation of alpha,beta-unsaturated ketones follow well established radical cyclization rules which is exemplified by studying the reactions of 39 and 40. Generality of these cyclizations is demonstrated from the PET reactions of 29-32. Synthesis of 49, an important structural framework of biologically active angularly fused triquinanes, from 48 is included in this study to demonstrate the varied applicability of this strategy.

  DOI：

  10.1021/ja9641564

文献信息

• Designing Photosystems for Harvesting Photons into Electrons by Sequential Electron-Transfer Processes:  Reversing the Reactivity Profiles of α,β-Unsaturated Ketones as Carbon Radical Precursor by One Electron Reductive β-Activation
  作者：Ganesh Pandey、Saumen Hajra、Manas K. Ghorai、K. Ravi Kumar

  DOI：10.1021/ja9641564

  日期：1997.9.1

  Two photosystems are developed to harvest visible-light photons into electrons via sequential electron transfer processes. Photosystem-A (PS-A) consisted of DCA as light harvesting electron acceptor and Ph3P as sacrificial electron donor, whereas photosystem-B (PS-B) employed DCA as usual electron acceptor, DMN as a primary electron donor, and ascorbic acid as a secondary and sacrificial election donor. alpha,beta-Unsaturated ketones are utilized as secondary electron acceptors. The design of these photosystems is based on the thermodynamic feasibility of electron transfer between each participating components. Electron transfer from DCA(.-) to alpha,beta-unsaturated ketones leads to their beta-activation as carbon centered radicals which cyclizes efficiently to tethered activated olefins. Cyclization with a nonactivated olefin is found to be moderate. The cyclization stereochemistries have been illustrated by studying the PET activation of 5 and 21. The exclusive trans-stereochemistry observed in 8 is explained by considering the thermodynamic, equilibration of initially formed syn-intermediate 10 from 5. The isolation of trace amount of 9 in this reaction substantiates the syn-intermediacy as primary intermediate which is further confirmed by the isolation of 25 from 21. Formation of 25 suggests that wherever the syn-intermediate is thermodynamically more stable, it invariably undergoes further cyclization to geometrically well-placed enolate double bond. An interesting observation is made by isolating 9 as a major product from the PET activation of 5 using PS-B. Stabilization of 10 by ascorbic acid is suggested to be the plausible explanation for this unusual observation. Radicals produced by the reductive beta-activation of alpha,beta-unsaturated ketones follow well established radical cyclization rules which is exemplified by studying the reactions of 39 and 40. Generality of these cyclizations is demonstrated from the PET reactions of 29-32. Synthesis of 49, an important structural framework of biologically active angularly fused triquinanes, from 48 is included in this study to demonstrate the varied applicability of this strategy.
• Synthesis of Tangutorine
  作者：Tse-Lok Ho、Chun-Kuei Chen

  DOI：10.1002/hlca.200690003

  日期：2006.1

  Tangutorine (1) in the racemic form has been assembled from tryptamine and aldehyde 3. The synthetic design was based on uncovering a hidden symmetry in the nontryptamine portion of the norketone 2. A five-step process with an overall yield of 7% was developed in which 2 was transformed into the target molecule via a Vilsmeier–Haack reaction and two reduction steps.

  外消旋形式的Tangutorine（1）由色胺和醛3组装而成。合成设计基于在甲酮2的非色胺部分中发现隐藏的对称性。用7％的总产率甲五个步骤中开发了其中2转化成目标分子通过一个维尔斯迈尔-哈克反应和两个还原步骤。