(E)-7-[2-(ethoxycarbonyl)ethenyl]-3-((ethoxycarbonyl)methyl)phthalide

• 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: (E)-7-[2-(ethoxycarbonyl)ethenyl]-3-((ethoxycarbonyl)methyl)phthalide
• 英文别名: (E)-ethyl 3-(1-(2-ethoxy-2-oxoethyl)-3-oxo-1,3-dihydroisobenzofuran-4-yl)acrylate；ethyl (E)-3-(1-(2-ethoxy-2-oxoethyl)-3-oxo-1,3-dihydroisobenzofuran-4-yl)acrylate；ethyl (E)-3-[1-(2-ethoxy-2-oxoethyl)-3-oxo-1H-2-benzofuran-4-yl]prop-2-enoate
• 化学式: C₁₇H₁₈O₆
• 分子量: 318.326
• InChiKey: HDSPLYBYZUPPHR-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  苯甲酸 、 丙烯酸乙酯 在 bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 copper diacetate 作用下， 反应 12.0h， 以86%的产率得到(E)-7-[2-(ethoxycarbonyl)ethenyl]-3-((ethoxycarbonyl)methyl)phthalide
  参考文献：
  名称：

  Ir(III)-Catalyzed Mono-Olefination of Aryl C–H Bonds Using −SCF₃ as a Weak Directing Group

  摘要：

  The trifluoromethylthionyl group (-SCF3) is an efficient weak directing group for Ir(III)-catalyzed aryl C-H olefination. Various trifluoromethylthioethers provide high levels of mono-olefination products in good to excellent yields under mild conditions with a 2,2'-bipyridine ligand or AgBF4 as an additive. Mechanistic studies indicate the C-H cleavage is the rate-determining step. The directing group ability of the -SCF3 group is benchmarked against several other weak directing groups by competition experiments under Ir(III)-catalyzed conditions.

  DOI：

  10.1021/acs.orglett.9b03125

文献信息

• One-Pot Sequential N-Heterocyclic Carbene/Rhodium(III) Catalysis: Synthesis of Fused Polycyclic Isocoumarins
  作者：So Won Youn、Huen Ji Yoo

  DOI：10.1002/adsc.201700072

  日期：2017.7.3

  A one‐pot sequential N‐heterocyclic carbene–rhodium (NHC‐Rh) catalysis is described, demonstrating the compatibility of NHC and Rh catalysts. N‐Heterocyclic carbene‐catalyzed aerobic oxidation of benzaldehydes and subsequent rhodium(III)‐catalyzed oxidative coupling/annulation with multiple bonds enabled the formation of two C–O bonds and one C–C bond in a single pot. This operationally easy, one‐pot

  描述了一个单锅顺序N-杂环卡宾-铑（NHC-Rh）催化，证明了NHC和Rh催化剂的相容性。N-杂环卡宾催化的苯甲醛好氧氧化，以及随后铑（III）催化的具有多个键的氧化偶联/环化反应，可在一个锅中形成两个C-O键和一个C-C键。这种易于操作的单罐协议在空气中提供了访问各种有价值的稠合多环异香豆素的途径。
• Synthesis of Phthalides through Tandem Rhodium-Catalyzed C-H Olefination and Annulation of Benzamides
  作者：Neeraj Kumar Mishra、Jihye Park、Miji Choi、Satyasheel Sharma、Hyeim Jo、Taejoo Jeong、Sangil Han、Saegun Kim、In Su Kim

  DOI：10.1002/ejoc.201600368

  日期：2016.6

  The rhodium(III)-catalyzed tandem C–H olefination and cyclization of benzamides with various alkenes is described. This protocol provides direct access to highly substituted phthalides, which are known as crucial frameworks of biologically active compounds. In particular, the amide directing group containing a benzimidazole group facilitates the activation of aromatic ortho-C–H bonds leading to olefination

  描述了铑 (III) 催化的串联 C-H 烯化和苯甲酰胺与各种烯烃的环化。该协议提供了对被称为生物活性化合物的关键框架的高度取代的苯酞的直接访问。特别是，含有苯并咪唑基团的酰胺导向基团促进芳族邻-C-H键的活化，导致烯化中间体，并迅速转化为酸部分，可以进一步进行分子内环化过程。
• Rhodium- and Iridium-Catalyzed Oxidative Coupling of Benzoic Acids with Alkynes via Regioselective C−H Bond Cleavage
  作者：Kenji Ueura、Tetsuya Satoh、Masahiro Miura

  DOI：10.1021/jo070735n

  日期：2007.7.1

  coupling of benzoic acids with internal alkynes effectively proceeds in the presence of [Cp*RhCl2]2 and Cu(OAc)2·H2O as catalyst and oxidant, respectively, to produce the corresponding isocoumarin derivatives. The copper salt can be reduced to a catalytic quantity under air. Interestingly, by using [Cp*IrCl2]2 in place of [Cp*RhCl2]2, the substrates undergo 1:2 coupling accompanied by decarboxylation to afford

  在[Cp * RhCl 2 ] 2和Cu（OAc）2 ·H 2 O作为催化剂和氧化剂的情况下，苯甲酸与内部炔烃的氧化偶联有效地进行，以产生相应的异香豆素衍生物。铜盐可以在空气中还原成催化量。有趣的是，通过使用[Cp * IrCl 2 ] 2代替[Cp * RhCl 2 ] 2，使底物进行1：2偶合并脱羧，从而仅得到萘衍生物。在这种情况下，Ag 2 CO 3作为有效的氧化剂。
• Urea‐Substituted Tetramethylcyclopentadienyl Ligands for Supramolecularly Accelerated Rh ^III ‐Catalyzed <i>ortho</i> ‐C−H Olefination of Benzoic Acid Derivatives
  作者：David Maurer、Bernhard Breit

  DOI：10.1002/chem.202005130

  日期：2021.2.5

  Through kinetic studies and NMR titration experiments, the catalysts’ substrate recognition ability mediated by hydrogen bonding was identified to be the reason for this effect. Introduction of pyridone‐phosphine ligands capable of forming additional H‐bond interactions increased the catalytic performance even further. By unveiling a proportionality between reaction rate and relative complex formation

  空气稳定且易于结晶的Rh III的设计与合成据报道，用脲部分取代的环戊二烯基催化剂能够促进苯甲酸衍生物的CHH烯化反应。通过动力学研究和NMR滴定实验，确定了氢键介导的催化剂底物识别能力是造成这种效应的原因。能够形成额外的H键相互作用的吡啶酮-膦配体的引入进一步提高了催化性能。通过揭示反应速率和相对复杂的形成焓之间的比例关系，支持了超分子催化剂预形成的假设。它在多种基材上的应用证明了催化剂体系的优势，与广泛使用[RhCp * Cl 2 ]的结果相比，通常可以提高收率。2。
• An Efficient Waste-Free Oxidative Coupling via Regioselective C−H Bond Cleavage:  Rh/Cu-Catalyzed Reaction of Benzoic Acids with Alkynes and Acrylates under Air
  作者：Kenji Ueura、Tetsuya Satoh、Masahiro Miura

  DOI：10.1021/ol070406h

  日期：2007.3.1

  [structure: see text]. The direct oxidative coupling of benzoic acids with internal alkynes proceeds efficiently in the presence of a rhodium/copper catalyst system under air to afford the corresponding isocoumarin derivatives. The reaction forms no wastes except for water. Under similar conditions, the aerobic coupling with acrylates also takes place smoothly to produce 7-vinylphthalide derivatives

  [结构：见文字]。在铑/铜催化剂体系的存在下，在空气中有效地进行苯甲酸与内部炔烃的直接氧化偶联，得到相应的异香豆素衍生物。除水外，该反应不形成废物。在相似的条件下，与丙烯酸酯的需氧偶联也可顺利进行，以通过二乙烯基化和随后的环化反应生成7-乙烯基邻苯二甲酸酯衍生物。