diethyl 2-(2-iodobenzyl)-2-(2-methylallyl)malonate | 1204606-36-9

• 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: diethyl 2-(2-iodobenzyl)-2-(2-methylallyl)malonate
• 英文别名: Diethyl 2-[(2-iodophenyl)methyl]-2-(2-methylprop-2-enyl)propanedioate
• CAS: 1204606-36-9
• 化学式: C₁₈H₂₃IO₄
• 分子量: 430.283
• InChiKey: QTOFJNDLLLAJJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  23
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2-(2-iodobenzyl)-2-(2-methylallyl)malonate 在 Pd(Q-Phos)₂ 作用下， 以 甲苯 为溶剂， 反应 16.0h， 以78%的产率得到4-iodomethyl-4-methyl-3,4-dihydro-1H-naphthalene-2,2-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Palladium-Catalyzed Carboiodination of Alkenes: Carbon−Carbon Bond Formation with Retention of Reactive Functionality

  摘要：

  We report a palladium-catalyzed carbon carbon bond-forming reaction between aryl iodides and alkenes. In contrast to traditional cross-coupling reactions, two new bonds are formed, and all of the atoms in the starting materials are incorporated into the product. The use of a palladium catalyst with bulky phosphine ligands is found to be crucial for reactivity.

  DOI：

  10.1021/ja110377q
• 作为产物：
  描述：

  diethyl (2-iodobenzyl)malonate 、 3-氯-2-甲基丙烯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 0.33h， 以66%的产率得到diethyl 2-(2-iodobenzyl)-2-(2-methylallyl)malonate
  参考文献：
  名称：

  Water-Controlled Regioselectivity of Pd-Catalyzed Domino Reaction Involving a C−H Activation Process: Rapid Synthesis of Diverse Carbo- and Heterocyclic Skeletons

  摘要：

  A palladium-catalyzed domino reaction involving a C-H activation process to synthesize diverse carbo- and heterocyclic skeletons was developed. H2O (as cosolvent) is used to control the regioselectivity.

  DOI：

  10.1021/ol902672a

文献信息

• Palladium-Catalyzed Three-Component Carbocarbonation of Arynes: Expeditious Synthesis of <i>o</i>-Alkylated Arylacrylates and Stilbenes
  作者：Tuanli Yao、Jiazhe Hui、Tao Liu、Tao Li

  DOI：10.1021/acs.joc.0c02994

  日期：2021.4.16

  A palladium-catalyzed multicomponent reaction involving olefin-tethered aryl iodides, arynes, and electrophilic alkenes has been developed for straightforward synthesis of o-alkylated arylacrylates and stilbenes through tandem intramolecular Heck cyclization/aryne dicarbofunctionalization.

  已经开发了涉及烯烃系链的芳基碘化物，芳烃和亲电烯烃的钯催化的多组分反应，用于通过串联的分子内Heck环化/芳烃二碳官能化直接合成邻烷基化的芳基丙烯酸酯和对苯二甲酸酯。
• Palladium‐Catalyzed Domino Synthesis of 2,3‐Difunctionalized Indoles <i>via</i> Migratory Insertion of Isocyanides in Batch and Continuous Flow
  作者：Su Chen、Monica Oliva、Luc Van Meervelt、Erik V. Van der Eycken、Upendra K. Sharma

  DOI：10.1002/adsc.202100339

  日期：2021.7

  We report, herein, a palladium-catalyzed cascade comprising carbopalladation, migratory insertion of isocyanide and triple bond activation followed by a nucleophilic attack (OR−) to construct difunctionalized acyl indoles. The process involves multiple bond formations via key palladium-chemistry steps, to construct these bis-heterocycles containing two privileged scaffolds (indole and oxindole) in

  我们在此报告了钯催化的级联反应，包括碳钯化、异氰化物的迁移插入和三键活化，然后是亲核攻击（OR -）以构建双官能化酰基吲哚。该过程涉及通过关键的钯化学步骤形成多个键，以在单个操作步骤中构建这些包含两个特权支架（吲哚和羟吲哚）的双杂环，并尝试在四元碳中心产生对映选择性。该方法还展示了在几分钟内合成芳基异氰化物并以伸缩方式使用它们的连续流动过程。
• Palladium-Catalyzed Disilylation and Digermanylation of Alkene Tethered Aryl Halides: Direct Access to Versatile Silylated and Germanylated Heterocycles
  作者：Marco Wollenburg、Jonathan Bajohr、Austin D. Marchese、Andrew Whyte、Frank Glorius、Mark Lautens

  DOI：10.1021/acs.orglett.0c01169

  日期：2020.5.1

  A method for the palladium-catalyzed disilylation and digermanylation of aryl halides bearing a tethered alkene has been developed. The mechanism is thought to proceed via Heck-type cyclization, followed by C-H activation, resulting in a reactive fused-palladacycle. A wide variety of disilylated and digermanylated heterocycles are obtained from readily available aryl halides in high yields with various

  已经开发了钯催化带有链状烯烃的芳基卤化物的二甲硅烷基化和二锗烷基化的方法。据认为，该机制是通过Heck型环化进行的，然后是CH活化，从而导致反应性稠合Palladacycle。从容易获得的具有各种官能团的芳基卤化物中获得了各种各样的二甲硅烷基化和二锗烷基化的杂环。此外，开发的协议被证明是高度非对映选择性的。
• Palladium-Catalyzed Domino Heck/Sulfination: Synthesis of Sulfonylated Hetero- and Carbocyclic Scaffolds Using DABCO–Bis(sulfur dioxide)
  作者：Jonathan Bajohr、Abdoul G. Diallo、Andrew Whyte、Sylvain Gaillard、Jean-Luc Renaud、Mark Lautens

  DOI：10.1021/acs.orglett.1c00716

  日期：2021.4.2

  The synthesis of a broad variety of hetero- and carbocyclic scaffolds via a Pd-catalyzed domino Heck/SO2 insertion reaction is reported. This reaction utilizes DABSO, a safe and easy-to-handle alternative to SO2 gas. The reaction proceeds through a sulfinate intermediate, which can act as a lynchpin for the in situ generation of sulfones, sulfonamides, and sulfonyl fluorides. Good yields and scalability

  据报道，通过Pd催化的多米诺骨牌Heck / SO 2插入反应可以合成各种各样的杂和碳环骨架。该反应利用了DABSO，它是SO 2气体的一种安全且易于操作的替代品。该反应通过亚磺酸盐中间体进行，该亚磺酸盐中间体可作为就地产生砜，磺酰胺和磺酰氟的关键。证明了良率和可伸缩性。
• Palladium-Catalyzed Domino Heck/C-H Activation/Intermolecular Direct Arylation Reactions
  作者：Yuxin Cui、Yanxing Jia、Zhiyao Lu

  DOI：10.1055/s-0030-1260603

  日期：2011.8

  A regioselective, palladium-catalyzed domino Heck/C-H activation/intermolecular direct arylation reaction has been developed, providing rapid access to diverse biaryl heterocycles. palladium - domino reaction - C-H activation - arylation

  已经开发了区域选择性的，钯催化的多米诺骨牌Heck / CH活化/分子间直接芳基化反应，可快速进入各种联芳基杂环。 钯-多米诺反应-CH活化-芳基化