3-(2,5-dimethylphenyl)acrylic acid ethyl ester | 356047-86-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 3-(2,5-dimethylphenyl)acrylic acid ethyl ester
• 英文别名: Ethyl 3-(2,5-dimethylphenyl)prop-2-enoate；ethyl 3-(2,5-dimethylphenyl)prop-2-enoate
• CAS: 356047-86-4
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: LOLGIHXPDIWKOI-UHFFFAOYSA-N

物化性质

• 沸点：
  300.2±11.0 °C(Predicted)
• 密度：
  1.024±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  对二甲苯 、 丙烯酸乙酯 在 3,5-bis(trifluoromethyl)pyridin-2(1H)-one 、 silver(I) acetate 、 palladium diacetate 作用下， 反应 24.0h， 以51%的产率得到3-(2,5-dimethylphenyl)acrylic acid ethyl ester
  参考文献：
  名称：

  配体加速的芳烃非定向 C-H 功能化

  摘要：

  碳氢键 (C-H) 的定向活化在合成有用反应的发展中很重要，因为通过配位官能团实现了邻近诱导的反应性和选择性。钯催化的非定向 C-H 活化有可能实现进一步有用的反应，因为它可以到达更远的位置并应用于不含适当定向基团的底物；然而，由于缺乏足够活性的钯催化剂，它的发展面临着巨大的挑战。目前使用的钯催化剂仅与富电子芳烃反应，除非使用过量的芳烃，这限制了合成应用。在这里，我们报告了一种 2-吡啶酮配体，它与钯结合并以芳烃为限制剂加速非定向 C-H 功能化。该协议与广泛的芳香底物兼容，我们展示了不能过量使用的高级合成中间体、药物分子和天然产物的直接功能化。我们还开发了 C-H 烯化和羧化方案，证明了我们的方法对其他转化的适用性。这些转化中的位点选择性受空间和电子效应的组合控制，吡啶酮配体增强了空间对选择性的影响，从而为定向 C-H 功能化提供了互补的选择性。该协议与广泛的芳香底物兼容，我们展示了不能

  DOI：

  10.1038/nature24632

文献信息

• Alkyne Hydroarylations with Chelating Dicarbene Palladium(II) Complex Catalysts: Improved and Unexpected Reactivity Patterns Disclosed Upon Additive Screening
  作者：Andrea Biffis、Luca Gazzola、Pierangelo Gobbo、Gabriella Buscemi、Cristina Tubaro、Marino Basato

  DOI：10.1002/ejoc.200900321

  日期：2009.7

  Palladium(II) complexes with a ligand set made from a chelating N-heterocyclic dicarbene ligand and two weakly coordinating anions (generally introduced in situ upon addition of 2 equiv. of a suitable silver salt) were found to be very active and selective catalysts for the room-temperature hydroarylation of alkynes at low catalyst loading (0.1 mol-%). Moreover, the screening of various strong acids

  发现钯 (II) 与由螯合 N-杂环双卡宾配体和两个弱配位阴离子（通常在添加 2 当量合适的银盐后原位引入）制成的配体组的配合物是非常活跃和选择性的催化剂在低催化剂负载量 (0.1 mol-%) 下炔烃的室温加氢芳基化。此外，各种强酸作为反应促进剂的筛选表明，酸的强度和其共轭碱的配位能力都会影响催化性能。最显着的是，HBF4 与二卡宾 Pd 络合物催化剂一起使用使反应的选择性发生了巨大变化，由于两分子炔烃插入芳族 C-H 键，产物的普遍形成。本文中呈现的结果强调了这样一个事实，即双卡宾配体除了稳定催化剂外，还能够提高催化活性，最值得注意的是，将反应选择性导向新产品。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Synthesis and Structure of 1,4-Diphenyl-3-methyl-1,2,3-triazol-5-ylidene Palladium Complexes and Application in Catalytic Hydroarylation of Alkynes
  作者：Rajendran Saravanakumar、Venkatachalam Ramkumar、Sethuraman Sankararaman

  DOI：10.1021/om1011984

  日期：2011.3.28

  An abnormal or mesoionic N-heterocyclic carbene (NHC), namely 1,4-diphenyl-3-methyl-1,2,3-triazol-S-ylidene (Tz), formed from 1,4-diphenyl-3-methyl-1,2,3-triazolium iodide and silver oxide, gave the corresponding silver carbene complex. The transmetalation reaction of the silver carbene complex with PdCl(2)(CH(3)CN)(2) gave a trans mononuclear complex, [(Tz)(2)PdCl(2)]. Reaction of the silver carbene complex with Pd(OAc)(2) gave an acetate-bridged binuclear complex in which the palladium had undergone a C-H insertion at the ortho position of the phenyl group attached to the triazole nitrogen (1-position). The structures of these two complexes Were established by single-crystal XRD data and spectroscopic data. The acetate complex was used as a catalyst for the stereoselective hydroarylation of alkynes.
• Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations
  作者：Hui Duan、Menghuan Li、Guanghui Zhang、James R. Gallagher、Zhiliang Huang、Yu Sun、Zhong Luo、Hongzhong Chen、Jeffrey T. Miller、Ruqiang Zou、Aiwen Lei、Yanli Zhao

  DOI：10.1021/acscatal.5b00569

  日期：2015.6.5

  The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modem organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.
• Ligand-accelerated non-directed C–H functionalization of arenes
  作者：Peng Wang、Pritha Verma、Guoqin Xia、Jun Shi、Jennifer X. Qiao、Shiwei Tao、Peter T. W. Cheng、Michael A. Poss、Marcus E. Farmer、Kap-Sun Yeung、Jin-Quan Yu

  DOI：10.1038/nature24632

  日期：2017.11

  challenges associated with the lack of sufficiently active palladium catalysts. Currently used palladium catalysts are reactive only with electron-rich arenes, unless an excess of arene is used, which limits synthetic applications. Here we report a 2-pyridone ligand that binds to palladium and accelerates non-directed C–H functionalization with arene as the limiting reagent. This protocol is compatible with

  碳氢键 (C-H) 的定向活化在合成有用反应的发展中很重要，因为通过配位官能团实现了邻近诱导的反应性和选择性。钯催化的非定向 C-H 活化有可能实现进一步有用的反应，因为它可以到达更远的位置并应用于不含适当定向基团的底物；然而，由于缺乏足够活性的钯催化剂，它的发展面临着巨大的挑战。目前使用的钯催化剂仅与富电子芳烃反应，除非使用过量的芳烃，这限制了合成应用。在这里，我们报告了一种 2-吡啶酮配体，它与钯结合并以芳烃为限制剂加速非定向 C-H 功能化。该协议与广泛的芳香底物兼容，我们展示了不能过量使用的高级合成中间体、药物分子和天然产物的直接功能化。我们还开发了 C-H 烯化和羧化方案，证明了我们的方法对其他转化的适用性。这些转化中的位点选择性受空间和电子效应的组合控制，吡啶酮配体增强了空间对选择性的影响，从而为定向 C-H 功能化提供了互补的选择性。该协议与广泛的芳香底物兼容，我们展示了不能