diethyl allyl(cinnamyl)malonate | 139566-47-5

• 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 allyl(cinnamyl)malonate
• 英文别名: diethyl (prop-2'-en-1'-yl)(3''-phenylprop-2''-en-1''-yl)propanedioate；(E)-diethyl 2-allyl-2-cinnamylmalonate；diethyl 2-[(E)-3-phenylprop-2-enyl]-2-prop-2-enylpropanedioate
• CAS: 139566-47-5
• 化学式: C₁₉H₂₄O₄
• 分子量: 316.397
• InChiKey: NAISISSXWDGNQZ-JLHYYAGUSA-N

物化性质

• 沸点：
  407.4±45.0 °C(Predicted)
• 密度：
  1.063±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  23
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.37
• 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 allyl(cinnamyl)malonate 在 lithium aluminium tetrahydride 、 三乙胺 、 sodium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 104.0h， 生成 Toluene-4-sulfonic acid (E)-2-allyl-5-phenyl-pent-4-enyl ester
  参考文献：
  名称：

  Ring-Closing Metathesis in Methanol and Water

  摘要：

  The ring-closing metathesis (RCM) of acyclic dienes in both methanol and water has been achieved through the use of water-soluble ruthenium alkylidenes. These alkylidenes react readily with acyclic olefins in protic solvents, but they do not cyclize alpha,omega-dienes because of the instability of the resulting methylidene. Successful cyclization has been achieved through simple substrate modification-incorporation of an olefin substituent allows cyclization to proceed in good yield. A methyl-substituted substrate was cyclized in 60% conversion in methanol, and the incorporation of a phenyl substituent resulted in nearly quantitative cyclization. Phenyl-substituted substrates are best suited for the reaction, as a more stable, active catalyst is regenerated upon each catalyst turnover. Using this methodology, 90% conversion of a water-soluble substrate to a substituted cyclopentene has been achieved in aqueous solution. This methodology has also been successfully applied to increase RCM yields in organic solvents.

  DOI：

  10.1021/jo981678o
• 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 allyl(cinnamyl)malonate
  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

• Study on the total synthesis of velbanamine: Chemoselective dioxygenation of alkenes with PIFA via a stop-and-flow strategy
  作者：Huili Liu、Kuan Zheng、Xiang Lu、Xiaoxia Wang、Ran Hong

  DOI：10.3762/bjoc.9.113

  日期：——

  5-hydroxymethyl-gamma-lactones were constructed after hydrolysis. This strategy also differentiates terminally substituted alkenes and constitutes a potentially novel synthetic approach for the efficient synthesis toward velbanamine.

  开发了一种“停止流动”策略，用于通过 PIFA 引发的环化对烯烃进行化学选择性双氧化。该方法针对仲二烯的去对称化反应，水解后构建了一系列取代的5-羟甲基-γ-内酯。该策略还区分了末端取代的烯烃，并构成了一种潜在的新颖合成方法，用于有效合成维巴纳胺。
• Phosphoramidite Ligands in Iridium-Catalyzed Allylic Substitution
  作者：Damien Polet、Alexandre Alexakis、Karine Tissot-Croset、Clémence Corminboeuf、Klaus Ditrich

  DOI：10.1002/chem.200501180

  日期：2006.4.24

  A new phosphoramidite ligand was used in the iridium-catalyzed allylic substitution reaction. This permitted high regio- and enantioselectivities on a wide variety of substrates and nucleophiles. Because of the stereospecificity of the reaction obtained by using branched substrates, a kinetic resolution reaction was attempted. The origin of the impressive efficiency of this ligand in terms of kinetics

  在铱催化的烯丙基取代反应中使用了新的亚磷酰胺配体。这允许在多种底物和亲核试剂上具有很高的区域和对映选择性。由于通过使用支链底物获得的反应的立体特异性，尝试进行动力学拆分反应。详细研究了该配体在动力学方面令人印象深刻的效率的起因，以及取代基在胺部分邻位中的作用。
• Ni-Catalyzed Asymmetric Cycloisomerization of Dienes by Using TADDOL Phosphoramidites
  作者：Christian Schmitz、Walter Leitner、Giancarlo Franciò

  DOI：10.1002/chem.201500352

  日期：2015.7.20

  3‐dioxolane‐4,5‐dimethanol (TADDOL)‐based phosphoramidites has been synthesized and applied in the Ni‐catalyzed cycloisomerization of different dienes. Through the systematic variation of the three structural motifs of the lead structure, that is, the amine moiety, the protecting group, and the aryl substituents, the ligand features could be optimized for the asymmetric cycloisomerization of the model substrate

  合成了基于α，α，α，α-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOL）的亚磷酰胺库，并将其用于Ni催化的不同二烯的环异构化。通过铅结构的三个结构基序（即胺部分，保护基和芳基取代基）的系统变化，可以优化配体特征，以使模型底物二烯丙基丙二酸二乙酯的不对称环异构化。新催化体系的底物范围已扩展到其他二烯丙基底物，包括不对称二烯。总体上具有高达13 500 h -1的极高活性，对五元外亚甲基亚环戊烷的选择性很高，对映选择性高达92％  ee 已经实现。
• Palladium-Catalyzed Cyclizations of 1,6-Dienes in the Presence of Lewis Acids
  作者：Chang Ho Oh、Jung Duk Kim、Je Wook Han

  DOI：10.1246/cl.2001.1290

  日期：2001.12

  Palladium-catalyzed cyclizations of several 1,6-dienes were accomplished by utilizing a catalytic amount of additives. Use of Lewis acids gave the endocyclic compounds, while use of silver(I) salts gave the exocyclic compounds.

  钯催化的几种1,6-二烯的环化反应通过使用催化量的添加剂完成。使用路易斯酸生成内环化合物，而使用银(I)盐则生成外环化合物。
• Stereoselective Nickel-Catalyzed Cycloisomerization of 1,6-Dienes
  作者：Christian Böing、Julia Hahne、Giancarlo Franciò、Walter Leitner

  DOI：10.1002/adsc.200800104

  日期：2008.5.5

  terminal position leading again to five-membered cyclic products in fair to very good yields. Cycloisomerization products were subjected to sequential hydroboration as well as hydrogenation of the exo-methylene functional group. Promising diastereoselectivities were achieved and these reaction sequences could be efficiently performed in a one-pot procedure.

  描述了基于[Ni（烯丙基）（cod）] [BARF]和Wilke的氮杂膦烯基全部-（R）-1的催化剂体系对1，6-二烯的高度立体选择性环异构化。从对称取代的1,6-二烯形成五元环状产物获得了前所未有的高对映体过量，最高可达91％。对于在末端位置取代的不对称1,6-二烯，也实现了较高的化学和区域选择性，从而再次以合理的非常高的收率获得了五元环状产物。环化异构化产物先后进行硼氢化和exo加氢-亚甲基官能团。实现了有希望的非对映选择性，并且这些反应序列可以一锅法高效进行。