(Z)-dimethyl-(4-methoxybenzoyl)-ethene-(4-dimethylamino-1-pyridino)-1,2-dicarboxylate | 1015253-25-4

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (Z)-dimethyl-(4-methoxybenzoyl)-ethene-(4-dimethylamino-1-pyridino)-1,2-dicarboxylate
• 英文别名: dimethyl (Z)-2-[4-(dimethylamino)pyridin-1-ium-1-yl]-3-(4-methoxybenzoyl)but-2-enedioate;trifluoromethanesulfonate
• CAS: 1015253-25-4
• 化学式: CF₃O₃S*C₂₁H₂₃N₂O₆
• 分子量: 548.494
• InChiKey: KDWCLPODJVZTDU-YBFBCAGJSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.54
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  152
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  (Z)-dimethyl-(4-methoxybenzoyl)-ethene-(4-dimethylamino-1-pyridino)-1,2-dicarboxylate 、 苯硫酚 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 1.0h， 生成 dimethyl-(4-methoxybenzoyl)-ethene-1,2-dicarboxylate-phenylsulfide 、 dimethyl-(4-methoxybenzoyl)-ethene-1,2-dicarboxylate-phenylsulfide
  参考文献：
  名称：

  Nucleophilic β-Oniovinylation:  Concept, Mechanism, Scope, and Applications

  摘要：

  Insertion of an electron-deficient alkyne A-C C-A (A = CO(2)Me) into the C-L(+) bond of an acyl-onio salt R-C(O)-L(+) (R = Ar, OAlk; L = 4-dimethylaminopyridine, PPh(3)) has for the first time been achieved in the presence of catalytic amounts of the nucleophile L. For R = OMe, a second insertion of the alkyne was observed. X-ray structures were obtained for a number of such -oniovinylation products. Depending on reaction conditions, preferentially E- or Z-stereochemistry was observed, the Z-isomer being the thermodynamically more stable. A mechanism for this novel insertion reaction is presented which accounts for the topology of the products and rationalizes the observed stereochemistry. The beta-onio-activated Michael systems thus generated represent a virtually unexplored class of compounds. The onio substituent in such compounds can be selectively replaced by a number of nucleophiles. Thus a series of Michael systems with donor functions in the beta-position is easily synthesized. These compounds represent a source for useful further transformations, for example, cyclizations to quinolones, thiochromones, and pyrazoles.

  DOI：

  10.1021/ja071316a
• 作为产物：
  描述：

  CF₃O₃S^(1-)*C₁₅H₁₇N₂O₂⁽¹⁺⁾ 、 丁炔二酸二甲酯 在 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以960 mg的产率得到(Z)-dimethyl-(4-methoxybenzoyl)-ethene-(4-dimethylamino-1-pyridino)-1,2-dicarboxylate
  参考文献：
  名称：

  Nucleophilic β-Oniovinylation:  Concept, Mechanism, Scope, and Applications

  摘要：

  Insertion of an electron-deficient alkyne A-C C-A (A = CO(2)Me) into the C-L(+) bond of an acyl-onio salt R-C(O)-L(+) (R = Ar, OAlk; L = 4-dimethylaminopyridine, PPh(3)) has for the first time been achieved in the presence of catalytic amounts of the nucleophile L. For R = OMe, a second insertion of the alkyne was observed. X-ray structures were obtained for a number of such -oniovinylation products. Depending on reaction conditions, preferentially E- or Z-stereochemistry was observed, the Z-isomer being the thermodynamically more stable. A mechanism for this novel insertion reaction is presented which accounts for the topology of the products and rationalizes the observed stereochemistry. The beta-onio-activated Michael systems thus generated represent a virtually unexplored class of compounds. The onio substituent in such compounds can be selectively replaced by a number of nucleophiles. Thus a series of Michael systems with donor functions in the beta-position is easily synthesized. These compounds represent a source for useful further transformations, for example, cyclizations to quinolones, thiochromones, and pyrazoles.

  DOI：

  10.1021/ja071316a