(E)-tetramethyl 3-methylenehexane-2,2,5,5-tetracarboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-tetramethyl 3-methylenehexane-2,2,5,5-tetracarboxylate
• 英文别名: Tetramethyl 1-methyl-2-methylidenepentane-1,1,4,4-tetracarboxylate
• 化学式: C₁₅H₂₂O₈
• 分子量: 330.335
• InChiKey: CKQPONVKEAIHMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  23
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  甲基丙二酸二甲酯 、 3-acetoxy-2-fluoro-propene 在 2,2'-联吡啶 、 [Pd(C₃H₅)(cod)]BF₄ 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 12.0h， 以76%的产率得到(E)-tetramethyl 3-methylenehexane-2,2,5,5-tetracarboxylate
  参考文献：
  名称：

  Palladium-Catalyzed Double Alkylation of 3-Aryl-2-fluoroallyl Esters with Malonate Nucleophiles through the Carbon–Fluorine Bond Cleavage

  摘要：

  The alkylation of (Z)-3-aryl-2-fluoroallyl acetate with the malonate anion by the [Pd(C3H5)(cod)]BF4/2,2'-bpy catalyst proceeds through the carbon fluorine bond cleavage, and 2 equiv of the malonate nucleophile was introduced to the allyl substrate.

  DOI：

  10.1021/ol500121z

文献信息

• On the Regiochemistry of Nucleophilic Attack on 2-Halo π-Allyl Complexes. 4. The Effect of Silver Acetate and Nucleophile Concentrations in Competitive Nucleophilic Attack with Malonate and Phenoxide Nucleophiles
  作者：Michael G. Organ、Elena A. Arvanitis、Stephen J. Hynes

  DOI：10.1021/jo034119c

  日期：2003.5.1

  under Pd catalysis to generate the 2-bromo Pd-pi-allyl complex (triphenylphosphine ligand), which alkylates with malonate nucleophile at the terminal position. The presence of acetate ion in the reaction mixture results in some malonate attack being redirected to the central carbon. The acetate ion can come from the ionization of 1-acetoxy-2-bromo-2-propene or by the addition of silver acetate to the

  在Pd催化下将2，3-二溴-1-丙烯或其碳酸烯丙酯类似物电离，生成2-溴Pd-π-烯丙基络合物（三苯基膦配体），后者在末端位置与丙二酸亲核试剂烷基化。反应混合物中乙酸根离子的存在导致某些丙二酸的攻击被重定向到中心碳。乙酸根离子可以来自1-乙酰氧基-2-溴-2-丙烯的电离或通过向反应混合物中添加乙酸银。向反应中添加酚盐离子也会引起相同的区域化学现象，尽管较硬的阴离子（如甲醇盐）不会发挥这种作用。
• On the regiochemistry of nucleophilic attack on 2-halo π-allyl complexes. Part 3: The electronic effect of phenoxide ion and the ligand
  作者：Michael G. Organ、Elena A. Arvanitis、Stephen J. Hynes

  DOI：10.1016/s0040-4039(02)02183-4

  日期：2002.12

  2,3-Dibromo-1-propene was subjected to competitive attack by malonate and different phenoxide nucleophiles in the presence of Pd substituted with monodentate or bidentate ligands. The presence of phenoxide promotes central carbon attack on the initially-formed 2-bromo Pd-pi-allyl complex by malonate in the presence of mono or bidentate ligands on Pd. However, bidentate ligands on Pd disfavour the attack of phenoxide, either at the central position or the terminal position of either of the two pi-ally complexes formed during the course of these di-additions. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Palladium-Catalyzed Double Alkylation of 3-Aryl-2-fluoroallyl Esters with Malonate Nucleophiles through the Carbon–Fluorine Bond Cleavage
  作者：Mitsuaki Yamamoto、Shunsuke Hayashi、Kazuki Isa、Motoi Kawatsura

  DOI：10.1021/ol500121z

  日期：2014.2.7

  The alkylation of (Z)-3-aryl-2-fluoroallyl acetate with the malonate anion by the [Pd(C3H5)(cod)]BF4/2,2'-bpy catalyst proceeds through the carbon fluorine bond cleavage, and 2 equiv of the malonate nucleophile was introduced to the allyl substrate.