(E)-3,7-dimethylocta-2,6-dien-1-yl 4-bromobenzoate | 1273558-09-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (E)-3,7-dimethylocta-2,6-dien-1-yl 4-bromobenzoate
• 英文别名: [(2E)-3,7-dimethylocta-2,6-dienyl] 4-bromobenzoate
• CAS: 1273558-09-0
• 化学式: C₁₇H₂₁BrO₂
• 分子量: 337.257
• InChiKey: DZZYLTXXLXPPPS-SDNWHVSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.35
• 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)-3,7-dimethylocta-2,6-dien-1-yl 4-bromobenzoate 在 N-甲基吡咯烷酮 、 2,2'-联吡啶 、 氯化镍二甲氧基乙烷 、 四丁基氯化铵 作用下， 以 N-甲基吡咯烷酮 为溶剂， 以72 %的产率得到(E)-3,7-dimethylocta-2,6-dien-1-yl 4-chlorobenzoate
  参考文献：
  名称：

  电化学驱动的镍催化不饱和卤化物和三氟甲磺酸酯衍生物的卤化

  摘要：

  联合实验和理论技术强调了电化学驱动的镍催化芳基卤化物卤素交换反应中的三个主要催化事件：Ar−X 氧化加成到 Ni(0) 物质上，首先生成 Ni(II)ArX，然后发生盐复分解与氯化物反应得到Ni(II)ArCl。后者被电化学氧化成 Ni(III) 物质，从而在还原消除时形成产物。

  DOI：

  10.1002/anie.202311165
• 作为产物：
  描述：

  4-溴苯甲酸 在 吡啶 、 氯化亚砜 作用下， 以 乙腈 为溶剂， 反应 16.0h， 生成 (E)-3,7-dimethylocta-2,6-dien-1-yl 4-bromobenzoate
  参考文献：
  名称：

  New Analogues of (E)-β-Farnesene with Insecticidal Activity and Binding Affinity to Aphid Odorant-Binding Proteins

  摘要：

  (E)-β-НАРСЕС is a strong and efficient ALARM PHENOMONE in most aphid species. However, its applications in agriculture are hindered by its relatively high VOLATILITY, susceptibility to OXIDATION, and complex and costly SYNTHESIS. In an effort to develop novel chemical entities for aphid CONTROL, we have designed and synthesized ANALOGUES of (E)-β-НАРСЕС, each bearing a PYRAZOLE moiety, a structural feature commonly found in several INSECTICIDES. Their structural analyses have been confirmed via (1)H NMR, ELEMENTAL ANALYSIS, HIGH-RESOLUTION MASS SPECTROSCOPY, and INFRARED SPECTROSCOPY. Binding activities to three ODDOR glVertex proteins (OBVs) of the pea aphid Acythosiphon pisum have been evaluated and correlative with the compounds' structures as a reference to (E)-β-НАРСЕС. Several derivatives were found to bind to A. pisum OBDs with a specificity comparable to that of (E)-β-НАРСЕС and exhibited ENTICING activity akin to that of thiacloprid, a widely used COMMERCIAL INSECTICIDE. The compounds synthesized in this study represent novel POTENTIAL AGENTS for POPULATION CONTROL of aphids and offer guidance for the design of ANALOGS of (E)-β-НАРСЕES endowed with both INSECTICIDAL and repellent properties for aphids.

  DOI：

  10.1021/jf104712c

文献信息

• Intermolecular C–H Amination of Complex Molecules: Insights into the Factors Governing the Selectivity
  作者：Camille Lescot、Benjamin Darses、Florence Collet、Pascal Retailleau、Philippe Dauban

  DOI：10.1021/jo301563j

  日期：2012.9.7

  appropriate tether securing intramolecular addition of the nitrene, the intermolecular C–H amination remains much less predictable. This study aims at addressing this issue by capitalizing on an efficient stereoselective nitrene transfer involving the combination of a chiral aminating agent 1 with a chiral rhodium catalyst 2. Allylic C–H amination of terpenes and enol ethers occurs with excellent yields as well

  过渡金属催化的氮杂胺插入导致的C–H胺化反应可将C–H直接转化为C–N键。考虑到有机化合物中C–H键的普遍存在，这种方法提出了区域选择性和化学选择性的问题，随着底物复杂性的提高，这一挑战性目标甚至更加难以解决。通过使用适当的系链确保在分子内添加氮烯可以实现出色的区域控制，而分子间CH胺化仍很难预测。这项研究旨在通过利用涉及手性胺化剂1和手性铑催化剂2的结合的有效立体选择性腈转移来解决这个问题。。由于空间和电子因素的结合，萜烯和烯醇醚的烯丙基CH氨化反应具有极高的收率，以及很高的区域选择性，化学选择性和非对映选择性。烯丙基CH键与π键的结合将解释对环状底物观察到的化学选择性。以化学计量的量使用的烷烃也可以有效地官能化，并且对三级赤道CH键具有网络偏好。在这种情况下，选择性可以通过空间和超共轭作用来合理化。因此，这项研究提供了有用的信息，可以更好地预测复杂分子的C–H胺化位点。
• Enantioselective Reductive <scp>Cross‐Coupling</scp> of Aryl/Alkenyl Bromides with Benzylic Chlorides <i>via</i> Photoredox/Biimidazoline Nickel Dual Catalysis
  作者：Tongtong Li、Xiaokai Cheng、Jiamin Lu、Huifeng Wang、Qun Fang、Zhan Lu

  DOI：10.1002/cjoc.202100819

  日期：2022.5

  The asymmetric reductive arylation and alkenylation of benzylic chloride under photoredox/nickel dual catalysis using chiral biimidazoline (BiIm) ligand is reported to access 1,1-diaryl alkanes and aryl allylic compounds with good yield as well as stereo- and enantioselectivities. This protocol uses more commercially available and less expensive C(sp2)-Br as the electrophile coupling partner. A primary

  据报道，使用手性双咪唑啉 (BiIm) 配体在光氧化还原/镍双重催化下对苄基氯进行不对称还原芳基化和烯基化反应，以良好的收率以及立体选择性和对映选择性获得 1,1-二芳基烷烃和芳基烯丙基化合物。该协议使用更商业化且更便宜的 C(sp 2 )-Br 作为亲电偶联伙伴。还报道了使用烯基氯和烷基氯的主要结果。可以容忍各种官能团，并通过后期官能化和克级反应研究该方法的应用。
• 一种手性1,5-二硼基烷烃化合物及其合成方法和应用
  申请人：浙江大学

  公开号：CN114957304A

  公开（公告）日：2022-08-30

  本发明公开了一种手性1,5‑二硼基烷烃化合物，如式III所示，并公开了其合成方法和应用。本发明提供的手性1,5‑二硼基烷烃可合成手性1,5‑二醇化合物，或者也可通过手性1,5‑二硼基烷烃，一锅法制备手性1,5‑二醇化合物。手性1,5‑二醇化合物通过一系列化学转化，可进一步合成市售药物丙莫拉克。本发明提供的手性1,5‑二硼基烷烃也可以合成多种手性1,5‑二官能团化产物，通过逐级选择性偶联反应，可以合成三芳基取代的戊烷，在医药领域和材料领域具有潜在的应用价值。
• Cobalt‐Catalyzed Asymmetric Sequential Hydroboration/Isomerization/Hydroboration of 2‐Aryl Vinylcyclopropanes
  作者：Chenhui Chen、Hongliang Wang、Tongtong Li、Dongpo Lu、Jiajing Li、Xie Zhang、Xin Hong、Zhan Lu

  DOI：10.1002/anie.202205619

  日期：2022.7.25

  Chiral 1,5-bis(boronates) were synthesized via an enantioselective cobalt-catalyzed sequential hydroboration/isomerization/hydroboration of vinylcyclopropanes through a trisubstituted alkene intermediate. These chiral 1,5-bis(boronates) were further converted into chiral 1,2,5-triaryl alkanes by an iterative Suzuki–Miyaura cross-coupling reaction with aryl halides.

  通过对映选择性钴催化的乙烯基环丙烷通过三取代烯烃中间体的顺序硼氢化/异构化/硼氢化合成手性 1,5-双（硼酸酯）。这些手性 1,5-双（硼酸盐）通过与芳基卤化物的迭代 Suzuki-Miyaura 交叉偶联反应进一步转化为手性 1,2,5-三芳基烷烃。
• New Analogues of (<i>E</i>)-β-Farnesene with Insecticidal Activity and Binding Affinity to Aphid Odorant-Binding Proteins
  作者：Yufeng Sun、Huili Qiao、Yun Ling、Shaoxiang Yang、Changhui Rui、Paolo Pelosi、Xinling Yang

  DOI：10.1021/jf104712c

  日期：2011.3.23

  (E)-beta-Farnesene is a strong and efficient alarm pheromone in most aphid species. However, applications in agriculture are prevented by its relatively high volatility, its susceptibility to oxidation and its complex and expensive synthesis. To develop novel compounds for aphid control, we have designed and synthesized analogues of (E)-beta-famesene, containing a pyrazole moiety present in several insecticides. Their structures have been confirmed by (1)H NMR, elemental analysis, high-resolution mass spectroscopy and IR. Binding activities to three odorant-binding proteins (OBPs) of the pea aphid Acythosiphon pisum have been evaluated and correlated with their structures with reference to (E)-beta-famesene. Several derivatives were shown both to bind to A. pisum OBPs with a specificity similar to that of (E)-beta-famesene and to have aphicidal activity comparable to that of thiacloprid, a commercial insecticide. The compounds synthesized in this work represent new potential agents for aphid population control and provide guidelines to design analogues of (E)-beta-famesene endowed with both insecticidal and repellent activity for aphids.

  (E)-β-НАРСЕС is a strong and efficient ALARM PHENOMONE in most aphid species. However, its applications in agriculture are hindered by its relatively high VOLATILITY, susceptibility to OXIDATION, and complex and costly SYNTHESIS. In an effort to develop novel chemical entities for aphid CONTROL, we have designed and synthesized ANALOGUES of (E)-β-НАРСЕС, each bearing a PYRAZOLE moiety, a structural feature commonly found in several INSECTICIDES. Their structural analyses have been confirmed via (1)H NMR, ELEMENTAL ANALYSIS, HIGH-RESOLUTION MASS SPECTROSCOPY, and INFRARED SPECTROSCOPY. Binding activities to three ODDOR glVertex proteins (OBVs) of the pea aphid Acythosiphon pisum have been evaluated and correlative with the compounds' structures as a reference to (E)-β-НАРСЕС. Several derivatives were found to bind to A. pisum OBDs with a specificity comparable to that of (E)-β-НАРСЕС and exhibited ENTICING activity akin to that of thiacloprid, a widely used COMMERCIAL INSECTICIDE. The compounds synthesized in this study represent novel POTENTIAL AGENTS for POPULATION CONTROL of aphids and offer guidance for the design of ANALOGS of (E)-β-НАРСЕES endowed with both INSECTICIDAL and repellent properties for aphids.