Bicyclo[2.2.1]hept-2-ene, 5-ethenyl-6-methylene- | 110919-83-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: Bicyclo[2.2.1]hept-2-ene, 5-ethenyl-6-methylene-
• 英文别名: Bicyclo[2.2.1]hept-2-ene, 5-ethenyl-6-methylene-, (1R,4S,5S)-rel-；5-methylene-6-vinylnorbornene
• CAS: 110919-83-0；137105-19-2；137105-20-5
• 化学式: C₁₀H₁₂
• 分子量: 132.205
• InChiKey: SOHXASSJGKKLDE-UTLUCORTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  10.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  乙酸烯丙酯 、 2,5-降冰片二烯 在 bis(acetylacetonate)nickel(II) 、 三异丙基亚磷酸酯 、 三乙基铝 作用下， 以 异丙醇 、 甲苯 为溶剂， 反应 4.0h， 生成 Bicyclo[2.2.1]hept-2-ene, 5-ethenyl-6-methylene- 、 (1R,2R,5S,6S)-3-Methylene-tricyclo[4.2.1.0^2,5]non-7-ene
  参考文献：
  名称：

  Cooligomerization of allyl acetate with norbornadiene and its derivatives catalyzed by nickel complexes

  摘要：

  DOI：

  10.1007/bf00953863

文献信息

• Hydride transfer mechanism in the catalytic allylation of norbornadiene with allyl formate
  作者：S. A. Durakov、R. S. Shamsiev、V. R. Flid、A. E. Gekhman

  DOI：10.1007/s11172-018-2361-7

  日期：2018.12

  formate in the presence of the palladium catalytic systems is characterized by several peculiarities associated with the new reaction route: hydroallylation (reductive allylation) occurs along with the traditional allylation (oxidative allylation). Both processes are considered from the single point of view, and the mechanism assuming different routes of the hydride transfer in the key intermediates

  在钯催化体系存在下，降冰片二烯与甲酸烯丙酯的烯丙基化具有与新反应路线相关的几个特性：水解烯丙基化（还原烯丙基化）与传统烯丙基化（氧化烯丙基化）一起发生。从单一的角度考虑这两个过程，并提出了假设关键中间体中氢化物转移路线不同的机制。使用氘代反应物证明氢化物转移可涉及烯丙基、降冰片烯基或甲酰基部分。在所有情况下，与钯相关的 β 位碳原子结合的氢原子在该步骤中被消除。
• Catalytic hydroallylation of norbornadiene with allyl formate
  作者：I. P. Stolyarov、A. E. Gekhman、I. I. Moiseev、A. Yu. Kolesnikov、E. M. Evstigneeva、V. R. Flid

  DOI：10.1007/s11172-007-0052-x

  日期：2007.2

  Norbornadiene (NBD) reacts with allyl esters All—OC(O)R (R = Me, But, Ph, CCl3, CF3) in acetonitrile solutions of palladium(0) complexes to give a mixture of four isomeric nontraditional allylation products and the corresponding carboxylic acids. Under similar conditions, the reaction of NBD with allyl formate in solutions of Pd0 and PdII complexes occurs selectively, resulting in the product of addition of the allyl fragment and the H atom to an NBD double bond, 5-allylbicyclo[2.2.1]hept-2-ene, and CO2. The hydroallylation of NBD is accompanied by catalytic addition of formic and acetic acids to one double bond of the diene to give bicyclo[2.2.1]hept-2-en-5-ol and nortricyclan-3-ol acetates and formates. Unlike most known palladium-based catalyst systems, these complexes exhibit catalytic activity also in the absence of phosphines.

  降冰片二烯（NBD）与烯丙基酯 All-OC(O)R（R = Me、But、Ph、CCl3、CF3）在钯（0）络合物的乙腈溶液中发生反应，生成四种异构非传统烯丙基化产物和相应羧酸的混合物。在类似条件下，NBD 与甲酸烯丙酯在 Pd0 和 PdII 复合物溶液中发生选择性反应，生成烯丙基片段和 H 原子与 NBD 双键、5-烯丙基双环[2.2.1]庚-2-烯和 CO2 相加的产物。在 NBD 水烯丙基化的同时，催化甲酸和乙酸加到二烯的一个双键上，生成双环[2.2.1]庚-2-烯-5-醇和去甲环-3-醇乙酸酯和甲酸酯。与大多数已知的钯基催化剂体系不同，这些复合物在没有膦的情况下也具有催化活性。
• The influence of the phosphine ligand nature on palladium catalysts in the norbornadiene allylation with allyl formate
  作者：S. A. Durakov、R. S. Shamsiev、V. R. Flid

  DOI：10.1007/s11172-021-3213-4

  日期：2021.7

  of the electronic and steric characteristics of phosphine ligands on the catalytic properties of palladium catalysts in the allylation of norbornadiene with allyl formate has been investigated. The activity and selectivity of catalysts formed in situ from palladium acetate and phosphines depend on the nature of the ligand. A certain lability of phosphine is required to achieve a high activity and the

  研究了膦配体的电子和空间特性对钯催化剂在降冰片二烯与甲酸烯丙酯的烯丙基化反应中催化性能的影响。由乙酸钯和膦原位形成的催化剂的活性和选择性取决于配体的性质。要求磷化氢具有一定的不稳定性以实现高活性和所需的反应选择性。此外，在钯的配位范围内，膦配体最多只能占据一个位置。配体的关键作用在 β-氢化物消除步骤中变得明显。确定了选择性生产5-亚甲基-6-乙烯基降冰片烯的条件。
• A possible way to control the course of hydride transfer in allylation of norbornadiene in the presence of palladium phosphine catalysts
  作者：V. R. Flid、S. A. Durakov、T. A. Morozova

  DOI：10.1007/s11172-016-1629-z

  日期：2016.11

  Features of allylation of norbornadiene (NBD) with allyl formate were investigated in the presence of Pd catalysts. In addition to the products of single or double allylation and hydroallylation of NBD, the products of secondary transformations, hydration and hydroformylation, have been found. An effect of triphenylphosphine on the reaction direction was studied.

  在 Pd 催化剂存在下研究了降冰片二烯 (NBD) 与甲酸烯丙酯烯丙基化的特征。除了NBD的单或双烯丙基化和加氢烯丙基化的产物外，还发现了二次转化、水合和加氢甲酰化的产物。研究了三苯基膦对反应方向的影响。
• New heterogenized catalytic systems in norbornadiene allylation
  作者：V. R. Flid、S. A. Durakov

  DOI：10.1007/s11172-018-2094-7

  日期：2018.3

  New heterogenizated catalysts for the allylation of norbornadiene (NBD) were prepared by the adsorption immobilization and surface assembly methods. The obtained catalysts were screened in the allylation of NBD, and the main technological parameters of the process were determined.

  通过吸附固定和表面组装方法制备了用于降冰片二烯（NBD）烯丙基化的新型多相催化剂。在NBD烯丙基化反应中对所得催化剂进行了筛选，确定了该工艺的主要工艺参数。