2-(3-methyl-2-buten-1-yl)-2-(2-propen-1-yl)malonic acid, diethyl ester | 408333-38-0

• 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: 2-(3-methyl-2-buten-1-yl)-2-(2-propen-1-yl)malonic acid, diethyl ester
• 英文别名: diethyl (3'-methylbut-2'-en-1'-yl)(prop-2''-en-1''-yl)propanedioate；2-allyl-2-(3-methylbut-2-enyl)malonic acid diethyl ester；diethyl 2-allyl-2-(3-methylbut-2-en-1-yl)malonate；diethyl 2-allyl-2-(3-methylbut-2-enyl)malonate；diethyl allyl (3-methylbut-2-en-1-yl)malonate；allyl-(3-methyl-but-2-enyl)-malonic acid diethyl ester；Diethyl 2-(3-methylbut-2-enyl)-2-prop-2-enylpropanedioate
• CAS: 408333-38-0
• 化学式: C₁₅H₂₄O₄
• 分子量: 268.353
• InChiKey: MAFLBLFCMZNUKC-UHFFFAOYSA-N

物化性质

• 沸点：
  287.5±35.0 °C(Predicted)
• 密度：
  0.987±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  2-(3-methyl-2-buten-1-yl)-2-(2-propen-1-yl)malonic acid, diethyl ester 在 C₂₉H₃₁F₃I₂N₂RuS 、 乙酸乙酯 作用下， 以 氘代苯 为溶剂， 生成 3-环戊烯-1,1-二甲酸二乙酯
  参考文献：
  名称：

  配位添加剂作为二碘潜烯烃复分解催化剂中的活性调节剂

  摘要：

  Ru-SCF 3 -I在高浓度下引发受阻底物的闭环复分解，而在低底物浓度和低催化剂负载下不发生反应。向反应混合物中加入乙酸乙酯可在催化剂负载量减少十倍的情况下引发反应。添加剂与金属中心配位并激活潜在的反式二碘催化剂。

  DOI：

  10.1002/cctc.202201690
• 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 2-(3-methyl-2-buten-1-yl)-2-(2-propen-1-yl)malonic acid, diethyl ester
  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

• Cobalt-catalyzed cyclization with the introduction of cyano, acyl and aminoalkyl groups
  作者：Hiroto Hori、Shigeru Arai、Atsushi Nishida

  DOI：10.1039/c9ob00637k

  日期：——

  An efficient synthesis of carbo- and heterocycles using CC, CO and CN bonds under cobalt catalysis is described. The substituents on olefins are key for controlling the regio- and chemoselectivity in the initial hydrogen atom transfer step and quaternary carbons are efficiently constructed under mild conditions. Cyclopropane cleavage and tandem cyclization give highly functionalized bicyclic skeletons

  描述了在钴催化下利用C C，C O和C N键有效合成碳环和杂环的方法。烯烃上的取代基是控制初始氢原子转移步骤中区域和化学选择性的关键，并且在温和条件下可以有效地构建季碳。环丙烷裂解和串联环化可在一次操作中得到高度官能化的双环骨架。
• Simple, Chemoselective, Catalytic Olefin Isomerization
  作者：Steven W. M. Crossley、Francis Barabé、Ryan A. Shenvi

  DOI：10.1021/ja5105602

  日期：2014.12.3

  Catalytic amounts of Co(SaltBu,tBu)Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.

  催化量的 Co(SaltBu,tBu)Cl 和有机硅烷不可逆地使末端烯烃异构化一个位置。相同的催化剂影响二烯的环异构化和应变环的逆环异构化。可以耐受强路易斯碱（如胺和咪唑）和不稳定的官能团（如环氧化物）。
• Visible-Light-Controlled Ruthenium-Catalyzed Olefin Metathesis
  作者：Cédric Theunissen、Melissa A. Ashley、Tomislav Rovis

  DOI：10.1021/jacs.8b13663

  日期：2019.5.1

  development of a new system to achieve visible-light-controlled metathesis by merging olefin metathesis and photoredox catalysis. The combination of a ruthenium metathesis catalyst bearing two N-heterocyclic carbenes with an oxidizing pyrylium photocatalyst affords excellent temporal and spatial resolution using only visible light as stimulus. Applications of this system in synthesis, as well as in polymer

  烯烃复分解现在是创建新碳-碳键的最有效方法之一。虽然大多数努力都集中在开发更高效的催化剂上，但最近特别关注开发潜在的复分解催化剂，即需要外部刺激才能变得活跃的非活性物质。这提供了对反应的增强控制，这对于材料科学中的应用至关重要。在这里，我们报告了我们通过合并烯烃复分解和光氧化还原催化来实现可见光控制复分解的新系统的开发工作。带有两个 N-杂环卡宾的钌复分解催化剂与氧化性吡喃光催化剂的组合仅使用可见光作为刺激提供了出色的时间和空间分辨率。该系统在合成中的应用，
• Compositions And Methods For Visible-Light-Controlled Ruthenium-Catalyzed Olefin Metathesis
  申请人：The Trustees of Columbia University In The City of New York

  公开号：US20200108381A1

  公开（公告）日：2020-04-09

  The present disclosure provides compositions and methods for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, the composition comprising a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light.

  本公开提供了一种用于将第一烯基或炔基与第二烯基或炔基进行交换反应的组合物和方法，所述组合物包括一种钌交换催化剂和一种可被可见光激活的光还原催化剂。
• Carbon radical addition–cyclization reaction induced by ruthenium-photocatalyst under visible light irradiation
  作者：Eito Yoshioka、Shigeru Kohtani、Eri Tanaka、Yukari Hata、Hideto Miyabe

  DOI：10.1016/j.tet.2014.12.068

  日期：2015.2

  (i-Pr)2NEt, the photo-induced cascade radical addition–cyclization–trapping reaction proceeded in aqueous media. When i-C3F7I was employed as a radical precursor, the iodine atom-transfer radical cyclization proceeded even in the absence of (i-Pr)2NEt. Under the photo-induced conditions, ICH2CN and ICH2CF3 also worked well as carbon radical precursors. The photo-induced reductive electron-transfer to CF3SO2Cl

  在Ru（bpy）3 Cl 2 ·6H 2 O和（i -Pr）2 NEt存在下，光诱导的级联自由基加成-环化-捕集反应在水性介质中进行。当将i -C 3 F 7 I用作自由基前体时，即使不存在（i -Pr）2 NEt ，碘原子转移自由基的环化反应仍在进行。在光诱导条件下，ICH 2 CN和ICH 2 CF 3也可以作为碳自由基的前体。光诱导的还原电子转移至CF 3 SO 2Cl促进了氯原子转移自由基的环化。