1-(2-thienylmethanone)-ethene-1,2-bismethoxycarbonyl-(4-dimethylaminopyridinio) triflate | 1015253-33-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 1-(2-thienylmethanone)-ethene-1,2-bismethoxycarbonyl-(4-dimethylaminopyridinio) triflate
• 英文别名: (Z)-4-dimethylaminopyridino-(dimethyl-ethene-dicarboxylate)-(2-thienyl-methanone)-triflate；N-[2-(2-thienylcarbonyl)-1,2-di-(methoxycarbonyl)ethenyl]-4-dimethylaminopyridinio triflate；dimethyl (Z)-2-[4-(dimethylamino)pyridin-1-ium-1-yl]-3-(thiophene-2-carbonyl)but-2-enedioate;trifluoromethanesulfonate
• CAS: 1015253-33-4
• 化学式: CF₃O₃S*C₁₈H₁₉N₂O₅S
• 分子量: 524.496
• InChiKey: NNGNFUMYUFUMSH-BGWNKZQTSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  171
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为产物：
  描述：

  4-dimethylaminopyridinio-(2-thienylmethanone) triflate 、 丁炔二酸二甲酯 在 4-二甲氨基吡啶 作用下， 以 乙腈 为溶剂， 反应 72.0h， 以68.2%的产率得到1-(2-thienylmethanone)-ethene-1,2-bismethoxycarbonyl-(4-dimethylaminopyridinio) triflate
  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