2-Allyl-2-((Z)-but-2-enyl)-malonic acid dimethyl ester | 145429-72-7

• 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-Allyl-2-((Z)-but-2-enyl)-malonic acid dimethyl ester
• 英文别名: dimethyl 2-but-2-enyl-2-prop-2-enylpropanedioate
• CAS: 145429-72-7
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: ZEUMBEMTNAJWOR-UHFFFAOYSA-N

物化性质

• 沸点：
  232.3±35.0 °C(Predicted)
• 密度：
  1.017±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.86
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-Allyl-2-((Z)-but-2-enyl)-malonic acid dimethyl ester 在 二乙基硅烷 、 (2,6-C6H3(iPr)2)N=C(CH3)-C(CH3)=N(2,6-C6H3(iPr)2)2Ni2Br2 作用下， 反应 16.0h， 以59%的产率得到dimethyl trans-3-ethyl-4-methylcyclopentane-1,1-dicarboxylate
  参考文献：
  名称：

  Ni（I）催化的1,6-二烯的还原环化：机理控制的反式选择性

  摘要：

  Ni催化的1，6-二烯的还原环化得到具有高反式非对映选择性的3，4-二取代的环戊烷和吡咯烷衍生物。该环化反应使得能够有效合成反式3,4-二甲基gababutin，用于治疗神经性疼痛的药物铅，和反式- 3,4-二甲基吡咯烷，前体药物候选和杀虫剂。的反式选择性区分从经由氢原子转移和铅进行相关先例该反应的顺式产物。机械研究，包括动力学，光谱学和激进时钟研究，将反式归因于Ni（I）和Ni（III）中间体介导的经典有机金属催化循环的非对映选择性。与以前的Ni（II）催化剂观察到的氧化还原-中性环异构化相反，通过具有氧化还原活性的α-二亚胺配体稳定的富电子Ni（I）中间体对还原环化具有化学选择性。

  DOI：

  10.1016/j.chempr.2017.07.010
• 作为产物：
  描述：

  dimethyl 2-but-3-enyl-2-prop-2-enylpropane-1,3-dioate 在 n 作用下， 以 异丙醇 为溶剂， 反应 24.0h， 生成 2-Allyl-2-((Z)-but-2-enyl)-malonic acid dimethyl ester
  参考文献：
  名称：

  Ruthenium-Catalyzed Highly Efficient Intramolecular Olefin Coupling of α,ω-Dienes. Facile and Regioselective Synthesis of exo-Methylenecyclopentanes

  摘要：

  DOI：

  10.1021/jo982467m

文献信息

• Ruthenium(ii)-catalysed cycloisomerisation of 1,6-dienes by focused microwave dielectric heating: improved rates and selectivities leading to exo-methylenecyclopentanes
  作者：Ian J. S. Fairlamb、Gerard P. McGlacken、Felix Weissberger

  DOI：10.1039/b513798e

  日期：——

  We herein report the effect of microwave dielectric heating in the Ru-catalysed cycloisomerisation of 1,6-dienes. Substantially improved reaction rates are attained for a series of 1,6-diene substrates, with equivalent or higher isomeric purity than conventional thermal heating.

  我们在此报告了微波介电加热在钌催化的1,6-二烯环异构化中的影响。对于一系列1,6-二烯底物，反应速度显著提高，并且异构体纯度与传统热加热相当或更高。
• Palladium-Catalyzed Remote Diborylative Cyclization of Dienes with Diborons via Chain Walking
  作者：Shota Kanno、Fumitoshi Kakiuchi、Takuya Kochi

  DOI：10.1021/jacs.1c09705

  日期：2021.11.24

  A novel method for catalytic remote bismetalation of alkene substrates by the addition of dimetal reagents is accomplished by using chain walking. In the presence of a palladium catalyst, the reaction of various 1,n-dienes and diborons were converted into cyclopentane derivatives with two boryl groups at remote positions via facile regioselective transformation of an unactivated sp3 C–H bond to a C–B

  一种通过添加二金属试剂催化烯烃底物远程双金属化的新方法是通过使用链行走实现的。在钯催化剂的存在下，通过将未活化的 sp 3 C-H 键区域选择性转化为 C-B 键，各种 1， n-二烯和二硼的反应被转化为在远端位置具有两个硼基的环戊烷衍生物. 1, n-二烯(n≥7 )的反应实现了任何方法都难以实现的三个远距离键的顺序构建。
• Sodium p-toluenesulfinate/copper(II) acetate in free radical reactions
  作者：Chuang Che-Ping

  DOI：10.1016/s0040-4039(00)60961-9

  日期：1992.10

  A free radical reaction of alkenes with sodium p-toluenesulfinate/copper(II) acetate to give p-toluenesulfonyl group substituted alkenes, cyclopentane and tetralin systems is described.

  描述了烯烃与对甲苯磺酸钠/乙酸铜（II）的自由基反应，得到对甲苯磺酰基取代的烯烃，环戊烷和四氢化萘体系。
• Palladium-Catalyzed Hydroboration/Cyclization of 1,<i>n</i>-Dienes
  作者：Shota Kanno、Fumitoshi Kakiuchi、Takuya Kochi

  DOI：10.1021/acs.joc.2c02781

  日期：2023.2.17

  While the hydroboration of alkenes is well established, the corresponding cyclization reaction of dienes remains challenging. Here, we report a new method for hydroboration/cyclization applicable to various 1,n-dienes and hydroboranes. The method features the direct synthesis of borylalkyl cyclopentanes from common 1,6-dienes, which is highlighted by syntheses of elaborated pyrrolidine cores from easily

  虽然烯烃的硼氢化反应已经很成熟，但二烯的相应环化反应仍然具有挑战性。在这里，我们报告了一种适用于各种 1, n -二烯和氢硼烷的硼氢化/环化新方法。该方法的特点是从常见的 1,6-二烯直接合成硼烷基环戊烷，并通过从易于获得的二烯丙基胺合成精细的吡咯烷核来突出这一点。值得注意的是，1, n -二烯 ( n > 6) 也会形成五元环，提供“远程”硼氢化/环化，否则很难实现。
• Modular Catalysts for Diene Cycloisomerization:  Rapid and Enantioselective Variants for Bicyclopropane Synthesis
  作者：Jeremy A. Feducia、Alison N. Campbell、Michael Q. Doherty、Michel R. Gagné

  DOI：10.1021/ja064335d

  日期：2006.10.1

  Deconstructing the tridentate (triphos)Pt(II) first-generation catalysts into mixed diphosphine/monophosphine combinations (P2P) has led to new, more active catalysts for the cycloisomerization of 1,6-, and 1,7-dienes into bicyclo-[3.1.0] and -[4.1.0] products. When the diphosphine was the small bite angle dppm, reaction rates were similar to 20-fold faster than with triphos, although reaction rates and diastereoselectivities were also sensitive to the monophosphine (PMe3 being optimal for rate, PPh3 being optimal for selectivity). When the diphosphine was xyl-BINAP or SEGPHOS, the catalysts were enantioselective, and enantio-ratios up to 98:2 were observed. Both sets of catalysts showed enhanced functional group tolerance in comparison to the original (triphos)Pt2+ catalyst. X-ray structures for both precatalysts are also reported.