1,2,2-tri(methoxycarbonyl)ethenyltriphenylphosphinio triflate | 1015253-41-4

• 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: 1,2,2-tri(methoxycarbonyl)ethenyltriphenylphosphinio triflate
• 英文别名: (1,4-Dimethoxy-3-methoxycarbonyl-1,4-dioxobut-2-en-2-yl)-triphenylphosphanium;trifluoromethanesulfonate
• CAS: 1015253-41-4
• 化学式: CF₃O₃S*C₂₆H₂₄O₆P
• 分子量: 612.517
• InChiKey: FVGUTLBBUAXKEE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  145
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  4-二甲氨基吡啶 、 1,2,2-tri(methoxycarbonyl)ethenyltriphenylphosphinio triflate 以 二氯甲烷 为溶剂， 反应 16.0h， 以93.2%的产率得到Trifluoromethanesulfonate;trimethyl 2-[4-(dimethylamino)pyridin-1-ium-1-yl]ethene-1,1,2-tricarboxylate
  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：

  (methoxycarbonyl)triphenylphosphonium triflate 、 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 0.75h， 以2.330 g的产率得到1,2,2-tri(methoxycarbonyl)ethenyltriphenylphosphinio 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

文献信息

• Nucleophilic β-Oniovinylation:  Concept, Mechanism, Scope, and Applications
  作者：Robert Weiss、Matthias Bess、Stefan M. Huber、Frank W. Heinemann

  DOI：10.1021/ja071316a

  日期：2008.4.1

  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.