4,5-dimethoxy-2-nitrophenylacetic acid allyl ester | 1233875-84-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,5-dimethoxy-2-nitrophenylacetic acid allyl ester
• 英文别名: Prop-2-enyl 2-(4,5-dimethoxy-2-nitrophenyl)acetate
• CAS: 1233875-84-7
• 化学式: C₁₃H₁₅NO₆
• 分子量: 281.265
• InChiKey: WUDYQTNGVMIDHJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  90.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,5-dimethoxy-2-nitrophenylacetic acid allyl ester 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 为溶剂， 以73%的产率得到α-diazo-4,5-dimethoxy-2-nitrophenylacetic acid allyl ester
  参考文献：
  名称：

  α-Carboxy-6-nitroveratryl: A Photolabile Protecting Group for Carboxylic Acids

  摘要：

  The synthesis of a new photolabile protecting group for carboxylic acids, alpha-carboxy-6-nitroveratryl (alpha CNV), is described. Bromide 3, prepared in four steps from 3,4-dimethoxyphenylacetic acid, was used to alkylate carboxylic acids under mild conditions in good yield. Palladium-catalyzed deallylation afforded the acids 4a-h, which underwent rapid and quantitative photolysis at wavelengths longer than 300 nm to liberate the carboxylic acid in good to quantitative yield. The rate of photolysis and quantum yield were determined to be 325 s(-1) and 0.17.

  DOI：

  10.1021/jo100783v
• 作为产物：
  描述：

  4,5-二甲氧基-2-硝基苯乙酸 在 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 4,5-dimethoxy-2-nitrophenylacetic acid allyl ester
  参考文献：
  名称：

  钯催化硝基苯乙酸酯的 sp3−sp3 脱羧偶联

  摘要：

  硝基苯乙酸的烯丙酯容易发生钯催化的脱羧偶联。单硝基芳烃和二硝基芳烃底物都能产生高产率的偶联产物。此外，反应速率表明脱羧是限速的，并且空间上不利于获得脱羧反应构象的底物是不可行的。最后，将产物硝基芳烃还原成相应的苯胺，可以得到多种杂环，包括喹啉和二氢喹诺酮。

  DOI：

  10.1021/ja077070r

文献信息

• 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）。
• α-Carboxy-6-nitroveratryl: A Photolabile Protecting Group for Carboxylic Acids
  作者：Alexander G. Russell、Maria-Eleni Ragoussi、Rui Ramalho、Christopher W. Wharton、David Carteau、Dario M. Bassani、John S. Snaith

  DOI：10.1021/jo100783v

  日期：2010.7.2

  The synthesis of a new photolabile protecting group for carboxylic acids, alpha-carboxy-6-nitroveratryl (alpha CNV), is described. Bromide 3, prepared in four steps from 3,4-dimethoxyphenylacetic acid, was used to alkylate carboxylic acids under mild conditions in good yield. Palladium-catalyzed deallylation afforded the acids 4a-h, which underwent rapid and quantitative photolysis at wavelengths longer than 300 nm to liberate the carboxylic acid in good to quantitative yield. The rate of photolysis and quantum yield were determined to be 325 s(-1) and 0.17.
• Palladium-Catalyzed Decarboxylative sp³−sp³ Coupling of Nitrobenzene Acetic Esters
  作者：Shelli R. Waetzig、Jon A. Tunge

  DOI：10.1021/ja077070r

  日期：2007.12.1

  Allylic esters of nitrobenzene acetic acids undergo facile palladium-catalyzed decarboxylative coupling. Both mono- and dinitroarene substrates give high yields of the coupled products. Moreover, the rates of the reactions suggest that decarboxylation is rate-limiting and substrates that sterically disfavor attainment of the reactive conformation for decarboxylation are not viable. Finally, reduction

  硝基苯乙酸的烯丙酯容易发生钯催化的脱羧偶联。单硝基芳烃和二硝基芳烃底物都能产生高产率的偶联产物。此外，反应速率表明脱羧是限速的，并且空间上不利于获得脱羧反应构象的底物是不可行的。最后，将产物硝基芳烃还原成相应的苯胺，可以得到多种杂环，包括喹啉和二氢喹诺酮。