1-Ethyl hydrogen <<(E)-2,3-dihydro-2H-pyran-6-yl>methylene>succinate | 151697-28-8

• 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: 1-Ethyl hydrogen <<(E)-2,3-dihydro-2H-pyran-6-yl>methylene>succinate
• 英文别名: (E)-4-(3,4-dihydro-2H-pyran-6-yl)-3-ethoxycarbonylbut-3-enoic acid
• CAS: 151697-28-8
• 化学式: C₁₂H₁₆O₅
• 分子量: 240.256
• InChiKey: ONBMZFNNCFJVHO-VQHVLOKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-Ethyl hydrogen <<(E)-2,3-dihydro-2H-pyran-6-yl>methylene>succinate 在 草酰氯 作用下， 以 二氯甲烷 为溶剂， 以77%的产率得到Ethyl 5-hydroxy-7-chromancarboxylate
  参考文献：
  名称：

  烷氧基和环状醚氧具有不同的引导邻位锂化的能力

  摘要：

  的金属化图4a和图4b与Ñ动力学控制条件下正丁基锂（C 6 H ^ 6，20℃或Et 2 O，TMEDA（2当量），20℃）导致优选的脱质子化α到杂环。

  DOI：

  10.1016/s0040-4039(00)73670-7
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 在 叔丁基锂 作用下， 以 四氢呋喃 、 正戊烷 、 苯 为溶剂， 反应 1.5h， 生成 1-Ethyl hydrogen <<(E)-2,3-dihydro-2H-pyran-6-yl>methylene>succinate
  参考文献：
  名称：

  Relevance of Conformational Constraints to the Regioselective Lithiation of Aromatic Diethers. Application to the Convenient Construction of the DEF Tricyclic Subunit of the Austalides

  摘要：

  The lithiation of 29 and 30 is shown to occur at all three sites with a dissimilar kinetic preference. For the dihydrofuran, reaction at the proton labeled H-beta, operates predominantly; in the dihydropyran example, H-alpha is the favored site of deprotonation. These protons represent those that are the most deshielded in the respective H-1 NMR spectra. The same is true for 9 and 19, both of which undergo metalation adjacent to the ring oxygen. No crossover in regioselectivity is observed, presumably because the methoxy substituent is sterically precluded from rotating freely. Mixed complexes (dimers, etc.) or mixed aggregates in low equilibrium concentration are key to understanding the acidification phenomenon of ortho hydrogens. As a consequence of the dominance of regiocontrol by the ring oxygen in 9, a convenient means has been developed for elaboration of the tricyclic eastern sector of the austalide mycotoxins.

  DOI：

  10.1021/jo00087a018

文献信息

• Alkoxy and cyclic ether oxygens exhibit disparate capabilities for directing ortho lithiation
  作者：Leo A. Paquette、Matthias M. Schulze

  DOI：10.1016/s0040-4039(00)73670-7

  日期：1993.5

  Metalation of 4a and 4b with n-butyllithium under kinetically controlled conditions (C6H6, 20 °C or Et2O, TMEDA (2 equiv), 20 °C) leads to preferred deprotonation α to the heterocyclic ring.

  的金属化图4a和图4b与Ñ动力学控制条件下正丁基锂（C 6 H ^ 6，20℃或Et 2 O，TMEDA（2当量），20℃）导致优选的脱质子化α到杂环。
• Pequette, Leo A.; Schulze, Matthias M., Heterocycles, 1993, vol. 35, # 2, p. 585 - 589
  作者：Pequette, Leo A.、Schulze, Matthias M.

  DOI：——

  日期：——
• Relevance of Conformational Constraints to the Regioselective Lithiation of Aromatic Diethers. Application to the Convenient Construction of the DEF Tricyclic Subunit of the Austalides
  作者：Leo A. Paquette、Matthias M. Schulze、David G. Bolin

  DOI：10.1021/jo00087a018

  日期：1994.4

  The lithiation of 29 and 30 is shown to occur at all three sites with a dissimilar kinetic preference. For the dihydrofuran, reaction at the proton labeled H-beta, operates predominantly; in the dihydropyran example, H-alpha is the favored site of deprotonation. These protons represent those that are the most deshielded in the respective H-1 NMR spectra. The same is true for 9 and 19, both of which undergo metalation adjacent to the ring oxygen. No crossover in regioselectivity is observed, presumably because the methoxy substituent is sterically precluded from rotating freely. Mixed complexes (dimers, etc.) or mixed aggregates in low equilibrium concentration are key to understanding the acidification phenomenon of ortho hydrogens. As a consequence of the dominance of regiocontrol by the ring oxygen in 9, a convenient means has been developed for elaboration of the tricyclic eastern sector of the austalide mycotoxins.