1-(4-bromobenzyl) 2,2-diethyl ethene-1,2,2-tricarboxylate | 875665-04-6

• 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-(4-bromobenzyl) 2,2-diethyl ethene-1,2,2-tricarboxylate
• 英文别名: 2-O-[(4-bromophenyl)methyl] 1-O,1-O-diethyl ethene-1,1,2-tricarboxylate
• CAS: 875665-04-6
• 化学式: C₁₆H₁₇BrO₆
• 分子量: 385.211
• InChiKey: HTDWVTYIZYPNIW-UHFFFAOYSA-N

物化性质

• 沸点：
  415.9±35.0 °C(Predicted)
• 密度：
  1.404±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-(4-bromobenzyl) 2,2-diethyl ethene-1,2,2-tricarboxylate 、 2,4-二甲基吡咯 在 copper(II) bis(trifluoromethanesulfonate) 、 (S,S)-(-)-2,2'-异亚丙基双(4-叔丁基-2-恶唑啉) 作用下， 以 四氢呋喃 为溶剂， 生成 、
  参考文献：
  名称：

  Enantioselective Friedel–Crafts reactions of ethenetricarboxylates and substituted pyrroles and furans and intramolecular reaction of benzene derivatives

  摘要：

  Compared to enantioselective Friedel-Crafts reactions of indoles, reactions of alkylidene malonates with monocyclic aromatic compounds generally proceed with low enantioselectivity. The Friedel-Crafts reactions of ethenetricarboxylates 1 and monocyclic heteroaromatic compounds, such as substituted pyrroles and furans were investigated. The reaction of 1 with 2,4-dimethylpyrrole in the presence of a chiral bis-oxazoline-copper(II) complex (10 mol %) in tetrahydrofuran at room temperature gave alkylated products in up to 72% ee. The reaction of 1 with 2-substituted furans gave alkylated products in 46-62% ee. The absolute stereochemistry of the furan Friedel-Crafts product 7e was determined by transformation to the known 2,3-dimethylbutyric acid. The intramolecular reaction of benzene derivatives gave cyclized products up to 56% ee. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.05.016
• 作为产物：
  描述：

  4-溴苄醇 、 1,1-diethyl 2-hydrogen ethenetricarboxylate 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 生成 1-(4-bromobenzyl) 2,2-diethyl ethene-1,2,2-tricarboxylate
  参考文献：
  名称：

  Catalytic Enantioselective Friedel−Crafts/Michael Addition Reactions of Indoles to Ethenetricarboxylates

  摘要：

  The Friedel-Crafts reaction is an important reaction for the formation of new C-C bonds. Recently, catalytic enantioselective Friedel-Crafts reaction of alkylidene malonates has been reported. However, the substituents in alkylidene malonates are limited. To explore new substituents such as carboxyl and carbonyl groups, catalytic enantioselective Friedel-Crafts reactions of reactive ethenetricarboxylates and acyl-substituted methylenernalonates I were investigated. The reaction of 1 with indoles in the presence of catalytic amounts of chiral bisoxazoline copper(II) complex (10%) in THF at room temperature gave alkylated products in high yields and up to 95% ee. The enantioselectivity can be explained by the secondary orbital interaction on approach of indole to the less hindered side of the 1-Cu(II)-ligand complex.

  DOI：

  10.1021/jo052041p

文献信息

• Enantioselective Friedel–Crafts reactions of ethenetricarboxylates and substituted pyrroles and furans and intramolecular reaction of benzene derivatives
  作者：Shoko Yamazaki、Shinichi Kashima、Taiki Kuriyama、Yuko Iwata、Tsumoru Morimoto、Kiyomi Kakiuchi

  DOI：10.1016/j.tetasy.2009.05.016

  日期：2009.6

  Compared to enantioselective Friedel-Crafts reactions of indoles, reactions of alkylidene malonates with monocyclic aromatic compounds generally proceed with low enantioselectivity. The Friedel-Crafts reactions of ethenetricarboxylates 1 and monocyclic heteroaromatic compounds, such as substituted pyrroles and furans were investigated. The reaction of 1 with 2,4-dimethylpyrrole in the presence of a chiral bis-oxazoline-copper(II) complex (10 mol %) in tetrahydrofuran at room temperature gave alkylated products in up to 72% ee. The reaction of 1 with 2-substituted furans gave alkylated products in 46-62% ee. The absolute stereochemistry of the furan Friedel-Crafts product 7e was determined by transformation to the known 2,3-dimethylbutyric acid. The intramolecular reaction of benzene derivatives gave cyclized products up to 56% ee. (C) 2009 Elsevier Ltd. All rights reserved.
• Catalytic Enantioselective Friedel−Crafts/Michael Addition Reactions of Indoles to Ethenetricarboxylates
  作者：Shoko Yamazaki、Yuko Iwata

  DOI：10.1021/jo052041p

  日期：2006.1.1

  The Friedel-Crafts reaction is an important reaction for the formation of new C-C bonds. Recently, catalytic enantioselective Friedel-Crafts reaction of alkylidene malonates has been reported. However, the substituents in alkylidene malonates are limited. To explore new substituents such as carboxyl and carbonyl groups, catalytic enantioselective Friedel-Crafts reactions of reactive ethenetricarboxylates and acyl-substituted methylenernalonates I were investigated. The reaction of 1 with indoles in the presence of catalytic amounts of chiral bisoxazoline copper(II) complex (10%) in THF at room temperature gave alkylated products in high yields and up to 95% ee. The enantioselectivity can be explained by the secondary orbital interaction on approach of indole to the less hindered side of the 1-Cu(II)-ligand complex.