n-butyl 3-(2,6-dimethoxypyridin-3-yl)acrylate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: n-butyl 3-(2,6-dimethoxypyridin-3-yl)acrylate
• 英文别名: (E)-Butyl 3-(2,6-dimethoxypyridin-3-yl)acrylate；butyl (E)-3-(2,6-dimethoxypyridin-3-yl)prop-2-enoate
• 化学式: C₁₄H₁₉NO₄
• 分子量: 265.309
• InChiKey: ZEBFAAUHUNOUPG-VQHVLOKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  57.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  丙烯酸丁酯 、 2,6-二甲氧基吡啶-3-羧酸 在 palladium(II) trifluoroacetate silver carbonate 作用下， 以 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以88%的产率得到n-butyl 3-(2,6-dimethoxypyridin-3-yl)acrylate
  参考文献：
  名称：

  Development of a Decarboxylative Palladation Reaction and Its Use in a Heck-type Olefination of Arene Carboxylates

  摘要：

  The development of a palladium-catalyzed decarboxylative coupling reaction of arene carboxylates with olefinic substrates is described. The optimized procedure for decarboxylative palladation employs Pd(O2CCF3)2 as catalyst (0.2 equiv) in the presence of Ag2CO3 (3 equiv) in the solvent 5% DMSO-DMF and proceeds at temperatures of 80-120 degrees C with a wide range of arene carboxylates and alkenes as substrates. The process is proposed to proceed by an initial Ar-SE reaction involving ipso attack of an electrophilic Pd(II) intermediate on an arene carboxylate to form an arylpalladium(II) species with loss of carbon dioxide. This intermediate is then proposed to react with an olefinic substrate by steps common to the Heck coupling process. Reoxidation of the liberated Pd(0) in situ is proposed to establish the catalytic cycle.

  DOI：

  10.1021/ja027523m

文献信息

• Role of Mono-N-protected Amino Acid Ligands in Palladium(II)-Catalyzed Dehydrogenative Heck Reactions of Electron-Deficient (Hetero)arenes: Experimental and Computational Studies
  作者：Xuefeng Cong、Huarong Tang、Chao Wu、Xiaoming Zeng

  DOI：10.1021/om400890p

  日期：2013.11.11

  We report here that mono-N-protected amino acids (MPAAs), an important environmentally compatible structural motif, enable acceleration of Pd(II)-catalyzed dehydrogenative Heck reactions between pyridines and electron-deficient arenes with simple alkenes, leading to diversely functionalized C3- or meta-selective alkenylated pyridines and benzenes via non-chelate-assisted C–H activation. A comprehensive

  我们在这里报告，单N保护的氨基酸（MPAAs），一种重要的环境相容性结构基序，能够加速Pd（II）催化的吡啶和电子不足的芳烃与简单烯烃之间的脱氢Heck反应，从而导致功能化的C3 -或meta通过非螯合物辅助的C–H活化选择性烯基化吡啶和苯。通过DFT计算进行的全面理论研究表明，MPAA配体的氨基支架通过最初的N–H活化容易地转化为X型配体，从而导致吡啶C–H裂解的活化障碍相对较低。然后，氨基的性质从X型配体转变为L型配体使得烯烃取代可以顺利进行，而羧基则可以形成分子内氢键，从而大大降低了碳pal触动的激活障碍。计算结果和动力学同位素效应测量结果支持了限速C–H活化，其机制涉及协同的金属化/去质子化途径，吸热值为31。
• Development of a Decarboxylative Palladation Reaction and Its Use in a Heck-type Olefination of Arene Carboxylates
  作者：Andrew G. Myers、Daisuke Tanaka、Michael R. Mannion

  DOI：10.1021/ja027523m

  日期：2002.9.1

  The development of a palladium-catalyzed decarboxylative coupling reaction of arene carboxylates with olefinic substrates is described. The optimized procedure for decarboxylative palladation employs Pd(O2CCF3)2 as catalyst (0.2 equiv) in the presence of Ag2CO3 (3 equiv) in the solvent 5% DMSO-DMF and proceeds at temperatures of 80-120 degrees C with a wide range of arene carboxylates and alkenes as substrates. The process is proposed to proceed by an initial Ar-SE reaction involving ipso attack of an electrophilic Pd(II) intermediate on an arene carboxylate to form an arylpalladium(II) species with loss of carbon dioxide. This intermediate is then proposed to react with an olefinic substrate by steps common to the Heck coupling process. Reoxidation of the liberated Pd(0) in situ is proposed to establish the catalytic cycle.