4,4,9,9-tetracarboethoxy-1,6,11-dodecatriene

• 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: 4,4,9,9-tetracarboethoxy-1,6,11-dodecatriene
• 化学式: C₂₄H₃₆O₈
• 分子量: 452.545
• InChiKey: DBPNXUDAXMRJIV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  32.0
• 可旋转键数：
  16.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  105.2
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  4,4,9,9-tetracarboethoxy-1,6,11-dodecatriene 、 尿素 在 sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 反应 12.0h， 以66%的产率得到
  参考文献：
  名称：

  Double Cyclopolymerization of Functionalized Trienes Catalyzed by Palladium Complexes

  摘要：

  Pd-diimine complexes catalyze polymerization of 1,6,11-dodecatrienes having cyclic ester groups at the 4 and 9 positions to produce the polymers containing two trans-five-membered rings in the structural units. The doublecyclopolymerization of triene with cyclic acetal group yields the polymer with narrow molecular weight distribution (M-w/M-n = 1.20-1.66). The two five-membered rings in a monomer unit of these polymers are linked directly with racemo stereochemistry. Relative stereochemistry of the monomer units separated by ethylene spacer changes depending on the monomer and catalyst, and 91% syndioselectivity is obtained in the polymerization of the triene with cyclic acetal groups. Hydrolysis of the polymer containing cyclic acetal groups yields the polymer containing CH2OH groups.

  DOI：

  10.1021/ma1022204

文献信息

• Ni-Catalyzed Reductive Dicarbofunctionalization of Nonactivated Alkenes: Scope and Mechanistic Insights
  作者：Wei Shu、Andrés García-Domínguez、M. Teresa Quirós、Rahul Mondal、Diego J. Cárdenas、Cristina Nevado

  DOI：10.1021/jacs.9b02973

  日期：2019.9.4

  bond. The role of the reductant was also investigated in depth, suggesting that a one-electron reduction of Ni(II) species to Ni(I) is thermodynamically favored. Further, the preferential activation of alkyl vs aryl halides by ArNi(I) complexes as well as the high affinity of ArNi(II) for secondary over tertiary C-centered radicals explains the lack of undesired homo- and direct coupling products (Ar-Ar

  没有导向或活化基团的烯烃在还原条件下用两个亲电碳源进行了双碳官能化。通过将 Ni 催化剂与作为牺牲还原剂的 TDAE 结合，在各种无偏 π 系统中同时形成一个 C(sp3)-C(sp3) 和一个 C(sp3)-C(sp2) 键，并具有极高的选择性。控制实验和计算研究揭示了基于自由基的机制的可行性，该机制涉及两个相互连接的 Ni(I)/Ni(III) 过程，并证明了 Ni(I) 物种（Ni(I)I 与 PhNi( I)) 以减少 C(sp3)-I 键。还深入研究了还原剂的作用，表明 Ni(II) 物质单电子还原为 Ni(I) 在热力学上是有利的。更多，
• Double Cyclopolymerization of Functionalized Trienes Catalyzed by Palladium Complexes
  作者：Kenya Motokuni、Takeshi Okada、Daisuke Takeuchi、Kohtaro Osakada

  DOI：10.1021/ma1022204

  日期：2011.2.22

  Pd-diimine complexes catalyze polymerization of 1,6,11-dodecatrienes having cyclic ester groups at the 4 and 9 positions to produce the polymers containing two trans-five-membered rings in the structural units. The doublecyclopolymerization of triene with cyclic acetal group yields the polymer with narrow molecular weight distribution (M-w/M-n = 1.20-1.66). The two five-membered rings in a monomer unit of these polymers are linked directly with racemo stereochemistry. Relative stereochemistry of the monomer units separated by ethylene spacer changes depending on the monomer and catalyst, and 91% syndioselectivity is obtained in the polymerization of the triene with cyclic acetal groups. Hydrolysis of the polymer containing cyclic acetal groups yields the polymer containing CH2OH groups.