(E)-2-(Benzo[1,3]dioxole-5-carbonyl)-3-(2,4,6-trimethoxy-phenyl)-acrylic acid methyl ester | 861215-28-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (E)-2-(Benzo[1,3]dioxole-5-carbonyl)-3-(2,4,6-trimethoxy-phenyl)-acrylic acid methyl ester
• 英文别名: methyl (E)-2-(1,3-benzodioxole-5-carbonyl)-3-(2,4,6-trimethoxyphenyl)prop-2-enoate
• CAS: 861215-28-3
• 化学式: C₂₁H₂₀O₈
• 分子量: 400.385
• InChiKey: GARRUEYYVBLVBR-XNTDXEJSSA-N

物化性质

• 沸点：
  601.9±55.0 °C(predicted)
• 密度：
  1.294±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (E)-2-(Benzo[1,3]dioxole-5-carbonyl)-3-(2,4,6-trimethoxy-phenyl)-acrylic acid methyl ester 在 [Ir(Me)(CO)(dppe)(DIB)][BArf4]2 作用下， 以 二氯甲烷-D2 为溶剂， 反应 0.13h， 以99%的产率得到5-Oxo-7-(2,4,6-trimethoxy-phenyl)-6,7-dihydro-5H-indeno[5,6-d][1,3]dioxole-6-carboxylic acid methyl ester
  参考文献：
  名称：

  Preorganization in the Nazarov cyclization: the role of adjacent coordination sites in the highly Lewis acidic catalyst [IrMe(CO)(dppe)(DIB)](BAr4f)2

  摘要：

  The dicationic Ir(III) complex [IrMe(CO)(dppe)(DIB)](BAr(4)(f))(2) where dppe = bis(diphenylphosphino)ethane and DIB = o-diiodobenzene possesses adjacent labile sites and is found to be a very active catalyst for the Nazarov cyclization. (31)P NMR spectroscopy provides evidence for substrate-catalyst binding by chelation, and this is found to be the resting state of the system during catalysis. The efficiency of the cyclization is attributed to the electrophilicity of the Ir(III) complex and substrate activation via O,O'-chelation which employs two substrate carbonyl group, or one carbonyl and an ether function, and encourages the s-trans/s-trans conformation required for cyclization. When two point binding occurs through an oxygen atom and one of the vinyl groups, the s-trans/s-trans conformation is not achieved. and cyclization is not observed. In one case, monodentate binding of substrate occurs, and the rate of cyclization is significantly slower than when O.O'-chelation is possible. The viability of O,O'-chelation is shown by the crystal structure determination of a model substrate-catalyst complex. (c) 2005 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tet.2005.03.114
• 作为产物：
  描述：

  2,4,6-三甲氧基苯甲醛 、 甲基β-氧代-1,3-苯并二氧杂环戊-5-丙酸乙酯 在 哌啶 、 溶剂黄146 作用下， 以 苯 为溶剂， 反应 1.0h， 生成 (E)-2-(Benzo[1,3]dioxole-5-carbonyl)-3-(2,4,6-trimethoxy-phenyl)-acrylic acid methyl ester
  参考文献：
  名称：

  极化纳扎罗夫环化：二烯酮取代模式对反应性和选择性的影响

  摘要：

  详细研究了二烯酮取代对 Nazarov 环化的影响。为了确定导致更高反应性和更好选择性的趋势，系统地探测了在二烯酮骨架的四个位置的每个位置上带有不同取代基的底物。发现通过在 C-2 和 C-4 位置放置极化基团使戊二烯基阳离子和氧烯丙基阳离子中间体去对称化特别有效。这些修饰允许在催化量的温和路易斯酸存在下发生环化。还发现亚烷基β-酮酯的E和Z异构体的混合物的立体会聚环化通过在反应条件下发生的有效异构化过程发生。

  DOI：

  10.1021/ja077162g

文献信息

• Preorganization in the Nazarov cyclization: the role of adjacent coordination sites in the highly Lewis acidic catalyst [IrMe(CO)(dppe)(DIB)](BAr4f)2
  作者：Mesfin Janka、Wei He、Alison J. Frontier、Christine Flaschenriem、Richard Eisenberg

  DOI：10.1016/j.tet.2005.03.114

  日期：2005.6

  The dicationic Ir(III) complex [IrMe(CO)(dppe)(DIB)](BAr(4)(f))(2) where dppe = bis(diphenylphosphino)ethane and DIB = o-diiodobenzene possesses adjacent labile sites and is found to be a very active catalyst for the Nazarov cyclization. (31)P NMR spectroscopy provides evidence for substrate-catalyst binding by chelation, and this is found to be the resting state of the system during catalysis. The efficiency of the cyclization is attributed to the electrophilicity of the Ir(III) complex and substrate activation via O,O'-chelation which employs two substrate carbonyl group, or one carbonyl and an ether function, and encourages the s-trans/s-trans conformation required for cyclization. When two point binding occurs through an oxygen atom and one of the vinyl groups, the s-trans/s-trans conformation is not achieved. and cyclization is not observed. In one case, monodentate binding of substrate occurs, and the rate of cyclization is significantly slower than when O.O'-chelation is possible. The viability of O,O'-chelation is shown by the crystal structure determination of a model substrate-catalyst complex. (c) 2005 Published by Elsevier Ltd.
• Polarizing the Nazarov Cyclization:  The Impact of Dienone Substitution Pattern on Reactivity and Selectivity
  作者：Wei He、Ildiko R. Herrick、Tulay A. Atesin、Patrick A. Caruana、Colleen A. Kellenberger、Alison J. Frontier

  DOI：10.1021/ja077162g

  日期：2008.1.1

  The impact of dienone substitution on the Nazarov cyclization has been examined in detail. Substrates bearing different substituents at each of four positions on the dienone backbone were systematically probed in order to identify trends leading to higher reactivity and better selectivity. Desymmetrization of the pentadienyl cation and oxyallyl cation intermediates through placement of polarizing groups

  详细研究了二烯酮取代对 Nazarov 环化的影响。为了确定导致更高反应性和更好选择性的趋势，系统地探测了在二烯酮骨架的四个位置的每个位置上带有不同取代基的底物。发现通过在 C-2 和 C-4 位置放置极化基团使戊二烯基阳离子和氧烯丙基阳离子中间体去对称化特别有效。这些修饰允许在催化量的温和路易斯酸存在下发生环化。还发现亚烷基β-酮酯的E和Z异构体的混合物的立体会聚环化通过在反应条件下发生的有效异构化过程发生。