(E)-1-pentyl-3-phenyl-2-propenyl acetate | 181036-39-5

• 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: (E)-1-pentyl-3-phenyl-2-propenyl acetate
• 英文别名: (E)-1-phenyloct-1-en-3-yl acetate；Amyl cinnamyl acetate；[(E)-1-phenyloct-1-en-3-yl] acetate
• CAS: 181036-39-5
• 化学式: C₁₆H₂₂O₂
• 分子量: 246.349
• InChiKey: PHOQNPPEIYLGSI-OUKQBFOZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1-pentyl-3-phenyl-2-propenyl acetate 在 四(三苯基膦)钯 、 (E)-hept-1-en-1-yl-1,3,2-benzodioxaborole 作用下， 以 苯 为溶剂， 反应 4.0h， 以70%的产率得到octa-1(E),3-dienylbenzene
  参考文献：
  名称：

  Nickel-Catalyzed Coupling Reaction of 1,3-Disubstituted Secondary Allylic Carbonates and Lithium Aryl- and Alkenylborates

  摘要：

  This account describes coupling reaction of 1,3-disubstituted secondary allylic carbonates with lithium aryl- and alkenylborates in the presence of a nickel. catalyst. Berates examined are 4, 5, and 6, and reactivity and selectivity were investigated using the allylic carbonates la and Ib. Coupling of la,b with berates 4 was effected with the nickel catalyst, NiCl2(PPh(3))(2) or NiCl2(dppf), in THF at 45-65 degrees C to provide products 3 in good yields with almost 100% regio- and stereoselectivities. Trivalent organoboranes prepared from acetylenes by hydroboration with catecholborane also underwent coupling reaction with la,b after transformation to berates 5 with MeLi. Though coupling using 4 and 5 required elevated temperature (45-65 degrees C), cyclic berates 6 prepared in situ from boronates 8 and MeLi were found to couple with la,b at room temperature or below. Regio- and stereoselectivities were almost 100% as were observed in the cases of 4 and 5. In these reactions, palladium complexes such as Pd(PPh(3))(4), Pd-2(dba)(3) . CHCl3 + 2 PPh(3) showed no catalytic activity. Stereochemical aspect of the present reaction was studied using cyclohexenyl carbonate 24 with 2-furylborate 4e and phenylborate 6a, and was found to proceed with overall anti fashion. With additional experiments, the mechanism of the present reaction was discussed in terms of transient pi-allylnickel intermediates.

  DOI：

  10.1021/jo960458c
• 作为产物：
  描述：

  1-辛烯-3-醇乙酸酯 、 benzenediazonium tetrafluoroborate 在 tris-(dibenzylideneacetone)dipalladium(0) 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 16.0h， 以87%的产率得到(E)-1-pentyl-3-phenyl-2-propenyl acetate
  参考文献：
  名称：

  电子无偏烯烃的操作简单且高度 (E)-苯乙烯基选择性 Heck 反应

  摘要：

  据报道，Pd(0) 催化的 Heck 反应采用简单、温和且有效的条件，该反应使用带有一系列有用功能的电子无偏烯烃底物，为 (E)-苯乙烯基产物提供高产率和选择性。初步机理研究表明，σ 供体 DMA 溶剂对于高选择性至关重要。进一步的研究表明，与之前报道的 Pd(II) 催化氧化反应条件相比，该催化剂根据它们的相对氢化特性来区分 β-氢。

  DOI：

  10.1021/ja203164p

文献信息

• PdII-Catalyzed Highly Selective Arylation of Allyl Esters via CH Functionalization of Unreactive Arenes with Retention of the Traditional Leaving Group
  作者：Delin Pan、Miao Yu、Wei Chen、Ning Jiao

  DOI：10.1002/asia.200900558

  日期：2010.5.3

  A highly selective Fujiwara–Moritani oxidative Heck reaction of allyl esters with unreactive arenes via CH bond activation was developed, in which β‐H elimination is highly chemo‐, regio‐ and stereoselective. Moreover, even electron‐deficient arenes are tolerated in this type of CH activation.

  通过C selective H键活化，开发了具有非反应性芳烃的烯丙基酯的高度选择性藤原-莫里塔尼氧化Heck反应，其中β-H消除具有高度的化学，区域和立体选择性。此外，这种CH活化作用甚至可以耐受电子缺乏的芳烃。
• Control of Chemo-, Regio-, and Stereoselectivities in Ligand-Free Pd-Catalyzed Oxidative Heck Reactions of Arylboronic Acids or Alkenylboronate with Allyl Esters
  作者：Yijin Su、Ning Jiao

  DOI：10.1021/ol9009865

  日期：2009.7.16

  ligand-free Pd-catalyzed highly selective oxidative Heck reaction of organoboronic acids with allyl esters was developed. β-H elimination is highly chemoselectively controlled, leading to γ-substituted allyl esters, which is contrary to the traditional Heck-type reactions of allyl esters. Moreover, the regio- and stereoselectivities are also high due to the chelation between O and Pd atoms.

  开发了无配体的Pd催化的有机硼酸与烯丙基酯的高选择性氧化Heck反应。β-H的消除是高度化学选择性控制的，导致生成γ-取代的烯丙基酯，这与烯丙基酯的传统Heck型反应相反。此外，由于O和Pd原子之间的螯合，区域和立体选择性也很高。
• Thiophene-Alkyne-Based CMPs as Highly Selective Regulators for Oxidative Heck Reaction
  作者：Ren-Hao Li、Zong-Cang Ding、Cun-Yao Li、Jun-Jia Chen、Yun-Bing Zhou、Xiao-Ming An、Yun-Jie Ding、Zhuang-Ping Zhan

  DOI：10.1021/acs.orglett.7b01858

  日期：2017.9.1

  as ligands for PdII-promoted organic reactions are reported for the first time. These ligands were utilized as catalytic sites and integrated into the skeleton of conjugated microporous polymers. By employing these CMP materials as selective regulators, oxidative Heck reactions between arylboronic esters and electronically unbiased alkenes provide highly selective linear products.

  首次报道了含有相邻的C≡C基团作为Pd II促进的有机反应的配体的噻吩。这些配体被用作催化位点并整合到共轭微孔聚合物的骨架中。通过将这些CMP材料用作选择性调节剂，芳基硼酸酯与电子无偏烯烃之间的氧化Heck反应可提供高度选择性的线性产物。
• Conjugated Microporous Polymer as Heterogeneous Ligand for Highly Selective Oxidative Heck Reaction
  作者：Yun-Bing Zhou、Yu-Qing Wang、Li-Chao Ning、Zong-Cang Ding、Wen-Long Wang、Cheng-Ke Ding、Ren-Hao Li、Jun-Jia Chen、Xin Lu、Yun-Jie Ding、Zhuang-Ping Zhan

  DOI：10.1021/jacs.7b00643

  日期：2017.3.22

  catalytic ligand for the PdII-catalyzed oxidative Heck reaction with high linear selectivity. The linear selectivity of CMP-1 is about 30 times higher than that of bipyridine-based monomer ligand. This work opens a new front of using CMP as an intriguing platform for developing highly efficient catalysts in controlling the regioselectivity in organic reactions.

  设计并合成了一系列含有 C≡C 键的吡啶型配体用于选择性氧化 Heck 反应。这些配体被用作功能单元并整合到共轭微孔聚合物的骨架中。6,6'-二碘-2,2'-联吡啶和1,3,5-三乙炔苯通过Sonogashira交叉偶联策略缩聚得到CMP-1材料。所得的 CMP-1 用作 PdII 催化的氧化 Heck 反应的多相催化配体，具有高线性选择性。CMP-1 的线性选择性比基于联吡啶的单体配体高约 30 倍。这项工作开辟了使用 CMP 作为开发高效催化剂控制有机反应区域选择性的有趣平台的新前沿。
• Constructing Mononuclear Palladium Catalysts by Precoordination/Solvothermal Polymerization: Recyclable Catalyst for Regioselective Oxidative Heck Reactions
  作者：Wen‐Hao Li、Cun‐Yao Li、Huan‐Yan Xiong、Yang Liu、Wen‐Yong Huang、Guang‐Jun Ji、Zheng Jiang、Hai‐Tao Tang、Ying‐Ming Pan、Yun‐Jie Ding

  DOI：10.1002/anie.201814493

  日期：2019.2.18

  Heterogeneous, metal, single‐site catalysts often exhibit higher catalytic performance than other catalysts because of their maximized atom efficiency of 100 %. Reported herein is a precoordination/solvothermal polymerization strategy to fabricate a stable mononuclear Pd‐metalized porous organic polymer catalyst (Pd@POP). Pd@POP was easy to use in regioselective organic reactions because the internal structure

  多相金属单中心催化剂通常具有比其他催化剂更高的催化性能，因为它们的最大原子效率为100％。本文报道了一种预配位/溶剂热聚合策略，以制备稳定的单核钯金属化多孔有机聚合物催化剂（Pd @ POP）。Pd @ POP易于在区域选择性有机反应中使用，因为该Pd @ POP的内部结构可以轻松进行修饰。该催化剂用于解决Heck反应难以解决的区域选择性问题。Pd @ POP-9可以有效地活化烯烃的末端，从而在外部位置具有较高的取代选择性。要了解催化剂高选择性和高活性的原因，进行了Pd @ POP-9的系统表征和密度泛函理论计算。这种Heck反应是第一个被具有可前所未有的催化活性和区域选择性的可回收单核金属催化剂催化的反应。