(E)-3-acetoxy-5-carbomethoxy-1-cyclohexene | 60729-56-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-3-acetoxy-5-carbomethoxy-1-cyclohexene
• 英文别名: trans-5-carbomethoxy-2-cyclohexen-1-yl acetate；trans-3-acetoxy-5-carbomethoxycyclohex-1-ene；trans-3-Acetoxy-5-carbomethoxy-1-cyclohexen；methyl (1S,5R)-5-acetyloxycyclohex-3-ene-1-carboxylate
• CAS: 60729-56-8
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: QMTVKLPUNFKWES-IUCAKERBSA-N

物化性质

• 沸点：
  248.6±40.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-3-acetoxy-5-carbomethoxy-1-cyclohexene 在 四(三苯基膦)钯 potassium tert-butylate 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 38.0h， 生成 dimethyl (Z)-(5-carbomethoxy-1-cyclohexen-3-yl)malonate
  参考文献：
  名称：

  Allylic alkylation. Palladium-catalyzed substitutions of allylic carboxylates. Stereo- and regiochemistry

  摘要：

  DOI：

  10.1021/ja00534a029
• 作为产物：
  描述：

  3-acetoxy-5-carbomethoxycyclohex-1-ene 在 吡啶 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 10.92h， 生成 (E)-3-acetoxy-5-carbomethoxy-1-cyclohexene
  参考文献：
  名称：

  Allylic alkylation. Palladium-catalyzed substitutions of allylic carboxylates. Stereo- and regiochemistry

  摘要：

  DOI：

  10.1021/ja00534a029

文献信息

• Structure and reactivity of cis- and trans-bis-[{5-carbomethoxy-(1,2,3-η)-cyclohexenyl}palladium]. Evidence for a (σ-allyl)palladium intermediate in the cis-migration of acetate from palladium to coordinated π-allyl
  作者：Helena Grennberg、Vratislav Langer、Jan-E. Bäckvall

  DOI：10.1039/c39910001190

  日期：——

  The mode of attack by acetate on a (π-allyl)palladium complex depends not only on the ligands on palladium, but also on the structure of the complexes; for the bis-[5-carbomethoxy-(1,2,3-η3)-cyclohexenyl}palladium] complexes, the structures of which were determined by X-ray crystallography and NMR spectroscopy, the cis isomer preferably reacted by external attack whereas the trans isomer, under identical

  乙酸盐对（π-烯丙基）钯配合物的攻击方式不仅取决于钯上的配体，而且取决于配合物的结构。对于双- [5-甲酯基（1,2,3-η 3）环己烯基}钯]络合物，其中通过X射线晶体学和NMR光谱法测定的结构中，顺式异构体优选由外部的攻击反应而在相同条件下，反式异构体则倾向于内部迁移。
• Cobalt‐Catalyzed Decarboxylative Allylations: Development and Mechanistic Studies
  作者：Ebbin Joseph、Rafael D. Hernandez、Jon A. Tunge

  DOI：10.1002/chem.202302174

  日期：2023.10.18

  In recent years, there has been a concerted drive to develop methods that are greener and more sustainable. Being an earth‐abundant transition metal, cobalt offers an attractive substitute for commonly employed precious metal catalysts, though reactions engaging cobalt are still less developed. Herein, we report a method to achieve the decarboxylative allylation of nitrophenyl alkanes, nitroalkanes, and ketones employing cobalt. The reaction allows for the formation of various substituted allylated products in moderate‐excellent yields with a broad scope. Additionally, the synthetic potential of the methodology is demonstrated by the transformation of products into versatile heterocyclic motifs. Mechanistic studies revealed an in situ activation of the Co(II)/dppBz precatalyst by the carboxylate salt to generate a Co(I)‐species, which is presumed to be the active catalyst.

  摘要 近年来，人们一直致力于开发更环保、更可持续的方法。钴是一种富含地球的过渡金属，可替代常用的贵金属催化剂，但目前利用钴进行的反应还不太成熟。在此，我们报告了一种利用钴实现硝基苯基烷、硝基烷和酮的脱羧烯丙基化的方法。该反应可生成各种取代的烯丙基化产物，产率适中，范围广泛。此外，该方法的合成潜力还体现在将产物转化为多功能杂环基团上。机理研究表明，Co(II)/dppBz 前催化剂被羧酸盐原位活化，生成了 Co(I)-species （推测为活性催化剂）。
• Organo tin nucleophiles iii. Palladium catalyzed reductive cleavage of allylic heterosubstituents with tin hydride
  作者：Ehud Keinan、Noam Greenspoon

  DOI：10.1016/s0040-4039(00)86797-0

  日期：1982.1
• Molybdenum(II)-Catalyzed Allylation of Electron-Rich Aromatics and Heteroaromatics
  作者：Andrei V. Malkov、Stuart L. Davis、Ian R. Baxendale、William L. Mitchell、Pavel Kočovský

  DOI：10.1021/jo982178y

  日期：1999.4.1

  The stable, readily available molybdenum(II) complexes [Mo(CO)(4)Br-2](2) (B) and Mo(CO)(3)(MeCN)(2)(SnCl3)Cl (C) have been found to catalyze C-C bond-forming allylic substitution with electron-rich aromatics (e.g., 15 + PhOMe --> 62) and heteroaromatics (e.g., 15 + 36 --> 88) as nucleophiles under mild conditions (room temperature, 30 min-3 h). Remarkable is the para-selectivity for anisole, whereas phenol tends to favor ortho-substitution in certain instances. Mechanistic and stereochemical experiments are indicative of Lewis-acid catalysis rather than a metal template-controlled process.
• Preparation of allylic acetates from simple alkenes by palladium(II)-catalyzed acetoxylation
  作者：Sverker Hansson、Andreas Heumann、Tobias Rein、Bjoern Aakermark

  DOI：10.1021/jo00290a031

  日期：1990.2