diethyl 2-allyl-2-benzylmalonate | 82044-44-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl 2-allyl-2-benzylmalonate
• 英文别名: Diethyl allyl(benzyl)malonate；diethyl 2-benzyl-2-prop-2-enylpropanedioate
• CAS: 82044-44-8
• 化学式: C₁₇H₂₂O₄
• 分子量: 290.359
• InChiKey: OWXQPIFYJSJUGL-UHFFFAOYSA-N

物化性质

• 沸点：
  228-230 °C(Press: 60-65 Torr)
• 密度：
  1.063±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 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-allyl-2-benzylmalonate 在 Fe(III)bis(imidazolonyl)pyridine)Cl₃ 三乙基铝 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以38%的产率得到苄基丙二酸二乙酯
  参考文献：
  名称：

  Fe-Catalyzed reactions of 2-chloro-1,7-dienes and allylmalonates

  摘要：

  Fe(III)(BIAP)Cl-3 complex catalyzes alkylative cyclization of 2-chloro-1,7-heptadiene in the presence of triethylaluminum. It also catalyzes deallylation of certain 2-allyl-2-substituted malonates under the same reaction conditions. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.04.143
• 作为产物：
  描述：

  二烯丙基丙二酸二乙酯 在 tris(triphenylphosphine)ruthenium(II) chloride 、 三乙基铝 、 sodium ethanolate 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 37.0h， 生成 diethyl 2-allyl-2-benzylmalonate
  参考文献：
  名称：

  Catalytic Deallylation of Allyl- and Diallylmalonates

  摘要：

  Substituted allylmalonates undergo the selective C-C bond cleavage in the presence of triethylaluminum and a catalytic amount of nickel and ruthenium phosphine complexes, resulting in the loss of the allyl moiety and formation of monosubstituted malonates. Comparison of reactivity of the nickel and ruthenium complexes showed that the use of the former is general with respect to the structure of the substituted allylmalonates, and the activity of the latter depended on the substitution pattern of the double bond of the allylic moiety. The smooth deallylation may encourage the use of the allyl group as a protective group for the acidic hydrogen in malonates.

  DOI：

  10.1021/ja047320t

文献信息

• Photoredox Catalyzed Intramolecular Fluoroalkylarylation of Unactivated Alkenes
  作者：Zuxiao Zhang、Henry Martinez、William R. Dolbier

  DOI：10.1021/acs.joc.6b03012

  日期：2017.3.3

  bond formation to an aryl ring is reported. The reactions are conducted under mild conditions and afford tetralin derivatives bearing difluoromethyl as well as other fluoroalkyl groups in good to high yields. In addition, the study indicates that 6-exo radical cyclization of an alkyl radical to a phenyl ring is faster than the respective 5-exo radical cyclization. A computational study provides insights

  据报道，第一个例子是光氧化还原催化未活化烯烃的二氟甲基化，并与形成芳基环的C-C键结合。该反应在温和的条件下进行，并以良好或高收率得到带有二氟甲基以及其他氟代烷基的四氢萘衍生物。另外，该研究表明，烷基至苯环的6-exo自由基环化比相应的5-exo自由基环化更快。计算研究为实验结果提供了见识。
• Intramolecular formal [4+2] cycloaddition of 3-ethoxycyclobutanones and alkenes
  作者：Jun-ichi Matsuo、Shun Sasaki、Takaya Hoshikawa、Hiroyuki Ishibashi

  DOI：10.1039/b919332d

  日期：——

  Intramolecular formal [4+2] cycloaddition between 3-ethoxycyclobutanones and a carbon-carbon double bond to the corresponding bicyclo[4.n.0]alkan-2-one derivatives proceeded effectively by using ethylaluminium dichloride.

  3-乙氧基环丁酮和碳-碳双键与相应的双环[4.n.0] alkan-2-one衍生物之间的分子内形式[4 + 2]环加成反应通过使用二氯化乙基铝有效地进行。
• Direct Allylation of Active Methylene Compounds with Allylic Alcohols by Use of Palladium/Phosphine-Borane Catalyst System
  作者：Aika Shimizu、Goki Hirata、Gen Onodera、Masanari Kimura

  DOI：10.1002/adsc.201800187

  日期：2018.5.16

  The C−C bond formation between active methylene compounds and allylic alcohols has been newly developed by using a palladium complex as a catalyst together with a phosphine‐borane ligand. The best phosphine‐borane ligand for this direct allylation has been revealed to be Ph2P(CH2)4(9‐BBN) to produce a variety of desirable allylated products in high yields.

  通过使用钯配合物与膦-硼烷配体作为催化剂，新开发了活性亚甲基化合物与烯丙基醇之间的C-C键形成。已经证明，用于这种直接烯丙基化的最佳膦硼烷配体是Ph 2 P（CH 2）4（9-BBN），可以高产率生产出各种理想的烯丙基化产物。
• Sustainable Palladium-Catalyzed Tsuji–Trost Reactions Enabled by Aqueous Micellar Catalysis
  作者：Nicholas R. Lee、Farbod A. Moghadam、Felipe C. Braga、Daniel J. Lippincott、Bingchun Zhu、Fabrice Gallou、Bruce H. Lipshutz

  DOI：10.1021/acs.orglett.0c01329

  日期：2020.7.2

  reactions, can be run under micellar catalysis conditions featuring not only chemistry in water but also numerous combinations of reaction partners that require low levels of palladium, typically on the order of 1000 ppm (0.1 mol %). These couplings are further characterized by especially mild conditions, leading to a number of cases not previously reported in an aqueous micellar medium. Inclusion of diverse

  钯催化的烯丙基取代或“ Tsuji–Trost”反应可在胶束催化条件下进行，该条件不仅具有水中的化学性质，而且具有需要低钯含量（通常约为1000 ppm（0.1）的反应伙伴的众多组合）摩尔％）。这些偶联的特征还在于特别温和的条件，导致许多以前在胶束水性介质中没有报道的病例。描述了包含各种亲核试剂，例如NH杂环，醇，二羰基化合物和磺酰胺。分子内环化进一步说明了该方法的广泛用途。除了回收研究之外，还报告了一个多克规模的示例，该示例表明了扩大规模的前景。
• Efficient Intramolecular Hydroarylation Catalysed by BiIII Triflate
  作者：Bastien Cacciuttolo、Sophie Poulain-Martini、Elisabet Duñach

  DOI：10.1002/ejoc.201100213

  日期：2011.7

  Non-activated aromatic compounds bearing unsaturated side-chains afford tetralin and benzosuberan derivatives in good yields in an atom-economic, environmentally friendly process catalysed by bismuth(III) trifluromethanesulfonate.

  带有不饱和侧链的未活化芳族化合物在三氟甲磺酸铋 (III) 催化的原子经济、环境友好的过程中以良好的收率提供四氢萘和苯并丁二烯衍生物。