2-(2-[1,3]dioxolan-2-yl-ethyl)-acrylic acid ethyl ester | 23985-07-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(2-[1,3]dioxolan-2-yl-ethyl)-acrylic acid ethyl ester
• CAS: 23985-07-1
• 化学式: C₁₀H₁₆O₄
• 分子量: 200.235
• InChiKey: QNPCJYCJHNQFFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.26
• 重原子数：
  14.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  44.76
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-(2-[1,3]dioxolan-2-yl-ethyl)-acrylic acid ethyl ester 在 盐酸 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 24.08h， 生成 ethyl (E)-2-methylidene-7-oxooct-5-enoate
  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：

  在 敌草腈 作用下， 以 苯 为溶剂， 以25%的产率得到2-(2-[1,3]dioxolan-2-yl-ethyl)-acrylic acid ethyl ester
  参考文献：
  名称：

  X = Y-ZH系统为潜在的1,3-偶极子。第34部分：由肟生成硝酮。串联迈克尔加成反应1，，3-偶极环加成反应。使用双功能迈克尔受体-双极性亲子组分的第2类方法。

  摘要：

  醛酮肟和酮肟通过涉及N-烯基硝酮中间体的串联过程与一系列包含官能化的1,3-，1,4-和1,5-二烯的双官能Michael受体-双极性亲和底物反应。1,3-二烯在区域和立体上发生特异性反应，生成1-氮杂-7-氧杂双环[2.2.1]庚烷，而空间上不受阻碍的芳基醛肟和1,4-二烯生成1-氮杂-2-氧杂双环[3.2]。 1]辛烷衍生物。1-Aza-2-oxa-和1-aza-8-oxa-双环[3.2.1]辛烷的酮肟和1.4消旋混合物。1,5-二烯和酮肟与区域和立体特异性反应，生成1-aza-8-氧杂双环[3.2.1]辛烷衍生物，而苯甲醛肟则生成1：1异构体的1-aza-8-氧杂双环[3.2]混合物。 1]辛烷以及两个差向异构的1-氮杂-2-氧杂双环[3.2.1]辛烷。串联过程的区域和立体化学结果受双功能底物中连接链的长度和性质以及在过渡状态下肟和双极性亲核体上取代基之间的空间相互作用所控制。据报道1-氮杂-7-氧杂双环[2

  DOI：

  10.1016/s0040-4020(01)91022-1

文献信息

• X=Y-ZH systems as potential 1,3-dipoles. Part 34. generation of nitrones from oximes. Tandem michael addition-1,3-dipolar cycloaddition reactions. class 2 processes utilising bifunctional michael acceptor-dipolarophile components.
  作者：Ronald Grigg、Michael J. Dorrity、Frances Heaney、John F. Malone、Shuleewan Rajviroongit、Visuvanathar Sridharan、Sivagnanasundram Surendrakumar

  DOI：10.1016/s0040-4020(01)91022-1

  日期：1991.9

  Aldoximes and ketoximes react with a range of bifunctional Michael acceptor-dipolarophile substrates comprising functionalised 1,3-, 1,4- and 1,5-dienes via a tandem process involving an N-alkenyl nitrone intermediate. The 1,3-dienes react regio- and stereo-specifically to give 1-aza-7-oxabicyclo[2.2.1]heptanes whilst sterically unencumbered aryl aldoximes and 1,4-dienes give 1-aza-2-oxabicyclo[3.2

  醛酮肟和酮肟通过涉及N-烯基硝酮中间体的串联过程与一系列包含官能化的1,3-，1,4-和1,5-二烯的双官能Michael受体-双极性亲和底物反应。1,3-二烯在区域和立体上发生特异性反应，生成1-氮杂-7-氧杂双环[2.2.1]庚烷，而空间上不受阻碍的芳基醛肟和1,4-二烯生成1-氮杂-2-氧杂双环[3.2]。 1]辛烷衍生物。1-Aza-2-oxa-和1-aza-8-oxa-双环[3.2.1]辛烷的酮肟和1.4消旋混合物。1,5-二烯和酮肟与区域和立体特异性反应，生成1-aza-8-氧杂双环[3.2.1]辛烷衍生物，而苯甲醛肟则生成1：1异构体的1-aza-8-氧杂双环[3.2]混合物。 1]辛烷以及两个差向异构的1-氮杂-2-氧杂双环[3.2.1]辛烷。串联过程的区域和立体化学结果受双功能底物中连接链的长度和性质以及在过渡状态下肟和双极性亲核体上取代基之间的空间相互作用所控制。据报道1-氮杂-7-氧杂双环[2
• 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.