2-(3,3-dimethoxypropyl)-cyclopentanone | 194496-29-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(3,3-dimethoxypropyl)-cyclopentanone
• 英文别名: 2-((3,3)-methoxypropyl)cyclopentanone；2-(3,3-Dimethoxypropyl)cyclopentan-1-one
• CAS: 194496-29-2
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: MMWUABBJXGGIDO-UHFFFAOYSA-N

物化性质

• 沸点：
  246.7±10.0 °C(Predicted)
• 密度：
  1.004±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(3,3-dimethoxypropyl)-cyclopentanone 在 盐酸 、 lithium aluminium tetrahydride 、 乙基溴化镁 作用下， 以 乙醚 、 水 、 丙酮 为溶剂， 反应 4.86h， 生成 3-(2-Hydroxy-2-propa-1,2-dienyl-cyclopentyl)-propionaldehyde
  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
• 作为产物：
  描述：

  1-溴-3,3-二甲氧基丙烷 、 N-cyclohexyl-N-cyclopentylidenamine 在 lithium diethylamide 、 氯化铵 作用下， 生成 2-(3,3-dimethoxypropyl)-cyclopentanone
  参考文献：
  名称：

  Ring-Enlarging Cyclohexane Annulations

  摘要：

  A Prins-pinacol rearrangement is the key step in a new method for synthesizing cis-bicyclo[n.4.0]alkanones. The alkenyl acetal rearrangement substrates 1 are assembled from cycloalkanone precursors in four steps (Table 1). Prins-pinacol rearrangement to form cis-bicyclo[n.4.0]alkanones 3 is best accomplished by exposure of 1 to 1 equiv of TMSOTf and a proton scavenger (2,6-di-tert-butyl-4-methylpyridine) at -78 degrees C --> rt.

  DOI：

  10.1021/jo970399i

文献信息

• Polycyclic oxonium ylides — Use of cyclic acetals as convenient scaffolds in the construction of fused bicyclic compounds containing a medium ring
  作者：Graham K Murphy、Fredrik P Marmsäter、F G West

  DOI：10.1139/v06-111

  日期：2006.10.1

  Cyclic mixed acetals with pendant diazoketone side chains undergo efficient rearrangement to ether-bridged cyclooctanoid and cycloheptanoid systems upon treatment with Cu(hfacac)2. Stevens [1,2]-sh...

  带有悬垂重氮酮侧链的环状混合缩醛在用 Cu(hfacac)2 处理后有效地重排为醚桥连的环辛烷和环庚烷系统。史蒂文斯 [1,2]-sh...
• Cyclooctanoid Ring Systems from Mixed Acetals via Heteroatom-Assisted [1,2]-Shift of Oxonium Ylides
  作者：Fredrik P. Marmsäter、Graham K. Murphy、F. G. West

  DOI：10.1021/ja0387249

  日期：2003.12.1

  efficient rearrangement to ether-bridged cyclooctanoid systems upon treatment with Cu(hfacac)2. This result demonstrates that heterosubstituted carbons are suitable migrating groups for the Stevens [1,2]-shift of oxonium ylides. In the case of a mixed thioacetal, the resulting sulfide served as a trigger for cleavage of the bridging ether through one of two complementary strategies, furnishing a bicyclo[6.3

  带有重氮酮侧链的环状混合缩醛在用 Cu(hfacac)2 处理后发生有效的重排，形成醚桥连的环辛烷系统。该结果表明，杂取代的碳是氧鎓叶立德的 Stevens [1,2] 位移的合适迁移基团。在混合硫缩醛的情况下，所得硫化物通过两种互补策略之一触发桥接醚裂解，提供具有角羟基的双环 [6.3.0] 辛烯产物。
• 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.
• Ring-Enlarging Cyclohexane Annulations
  作者：Sumie Ando、Keith P. Minor、Larry E. Overman

  DOI：10.1021/jo970399i

  日期：1997.9.1

  A Prins-pinacol rearrangement is the key step in a new method for synthesizing cis-bicyclo[n.4.0]alkanones. The alkenyl acetal rearrangement substrates 1 are assembled from cycloalkanone precursors in four steps (Table 1). Prins-pinacol rearrangement to form cis-bicyclo[n.4.0]alkanones 3 is best accomplished by exposure of 1 to 1 equiv of TMSOTf and a proton scavenger (2,6-di-tert-butyl-4-methylpyridine) at -78 degrees C --> rt.