(3-甲基丁-2-烯基)丙二酸二乙酯 | 22539-80-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: (3-甲基丁-2-烯基)丙二酸二乙酯
• 英文名称: diethyl (3-methylbut-2-enyl)malonate
• 英文别名: diethyl 2-(3-methylbut-2-en-1-yl)malonate；diethyl (3-methyl-2-butenyl)malonate；ethyl 2-ethoxycarbonyl-5-methyl-hex-4-enoate；diethyl 2-(3-methylbut-2-enyl)propanedioate
• CAS: 22539-80-6
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: UXBLYMUHQJDAFO-UHFFFAOYSA-N

物化性质

• 沸点：
  127 °C(Press: 11 Torr)
• 密度：
  0.9938 g/cm3(Temp: 18 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2917190090

反应信息

• 作为反应物：
  描述：

  (3-甲基丁-2-烯基)丙二酸二乙酯 在 lithium aluminium tetrahydride 、 正丁基锂 、 水 、 lithium chloride 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 6.75h， 生成 (1,5-Dimethyl-4-hexenylidene)-triphenylphosphorane
  参考文献：
  名称：

  Biosynthesis of (+)-epicubenol

  摘要：

  Incubation of [6-H-2]FPP (14a) with epicubenol synthase isolated from Streptomyces sp. LL-B7 gave epicubenol (1c) labeled at D-9 as established by 2H NMR. These results confirm the involvement of a predicted 1,2-hydride shift in the mechanism of formation of 1.

  DOI：

  10.1016/s0040-4039(00)73498-8
• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 在 dibromobis(triphenylphosphine)nickel(II) 三乙基铝 、 sodium ethanolate 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 25.0h， 生成 (3-甲基丁-2-烯基)丙二酸二乙酯
  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

• Calcium-Catalyzed Cycloisomerization of Enynes
  作者：Vera J. Meyer、Liang Fu、Fabian Marquardt、Meike Niggemann

  DOI：10.1002/adsc.201300253

  日期：2013.7.8

  A cycloisomerization of enynes with a benign calcium catalyst is presented exploring a complementary reactivity to that usually found in transition and noble metal‐catalyzed reactions. Thereby, a systematic investigation of the π‐activation of alkynes with reactive carbocations has been realized and ketones of various ring sizes were easily accessed. We are certain that these basic investigations will

  提出了利用良性钙催化剂对烯炔进行环异构化的方法，以探索与过渡和贵金属催化反应中通常发现的互补反应性。因此，已经实现了对带有反应性碳阳离子的炔烃的π-活化的系统研究，并且容易获得各种环大小的酮。我们相信，这些基础研究将为在贵金属催化领域发现的反应原理基础上的进一步反应铺平道路。
• Allylation of Active Methylene Compounds with Allyl Oxime Carbonates Catalyzed by Pd(0)
  作者：Osamu Suzuki、Yoshiharu Hashiguchi、Seiichi Inoue、Kikumasa Sato

  DOI：10.1246/cl.1988.291

  日期：1988.2.5

  Allylation of active methylene compounds catalyzed by a palladium(0)-phosphine system took place highly stereoselectively by employing allyl oxime carbonates as the allylating reagent.

  零价钯-膦配合物体系催化活性的甲川化合物与烯丙基肟碳酸酯进行高度立体选择性的烯丙基化反应。
• Angularly Fused Triquinanes from Linear Substrates through Trimethylenemethane Diyl [2 + 3] Cycloaddition Reaction
  作者：Hee-Yoon Lee、Yongsik Jung、Yeokwon Yoon、Byung Gyu Kim、Yeonjoon Kim

  DOI：10.1021/ol100907t

  日期：2010.6.4

  Angularly fused triquinanes were synthesized from linear dienes and phenyl(propynyl)iodonium salt through trimethylenemethane (TMM) diyl mediated [2 + 3] cycloaddition reaction. TMM diyl intermediates were obtained from alkylidene carbenes generated from reactions of alkynyliodonium salts with nucleophiles.

  通过三亚甲基甲烷（TMM）二基介导的[2 + 3]环加成反应，由直链二烯和苯基（丙炔基）碘鎓盐合成角熔融的三喹烷。TMM二烷基中间体是从炔烃鎓盐与亲核试剂反应生成的亚烷基卡宾获得的。
• Ruthenium-Catalyzed (2 + 2) Intramolecular Cycloaddition of Allenenes
  作者：Moisés Gulías、Alba Collado、Beatriz Trillo、Fernando López、Enrique Oñate、Miguel A. Esteruelas、José L. Mascareñas

  DOI：10.1021/ja200784n

  日期：2011.5.25

  We report a ruthenium-catalyzed (2 + 2) intramolecular cycloaddition of allenes and alkenes. We have found that the use of the ruthenium complex RuH(2)Cl(2)(P(i)Pr(3))(2), which has previously gone unnoticed in catalytic applications, is crucial for the observed reactivity. The reaction proceeds under mild conditions and is fully diastereoselective, providing a practical entry to a variety of bicyclo[3

  我们报告了钌催化的 (2 + 2) 丙二烯和烯烃的分子内环加成反应。我们发现使用钌复合物 RuH(2)Cl(2)(P(i)Pr(3))(2)，以前在催化应用中未被注意到，对观察到的反应性至关重要。该反应在温和的条件下进行并且完全非对映选择性，为各种具有环丁烷环的双环 [3.2.0] 庚烷骨架提供了实用的入口。
• Intramolecular reactions of allyloxy radicals featuring six-centred transition states; Regiochemistry and stereochemistry.
  作者：Michael J. Begley、Neil Housden、Amanda Johns、John A. Murphy

  DOI：10.1016/s0040-4020(01)96183-6

  日期：1991.9

  Intramolecular free-radical reactions of allyloxy radicals to form tetrahydropyrans and cyclopentanols have been studied; the cyclopentanols form stereoselectivety with irons disposition of groups about the ring-forming bond.

  已经研究了烯丙氧基自由基形成四氢吡喃和环戊醇的分子内自由基反应。环戊醇形成立体选择性，铁在成环键周围的基团被铁取代。