dimethyl 1-sodium-1-propargylmalonate | 107201-05-8

• 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: dimethyl 1-sodium-1-propargylmalonate
• 英文别名: sodium dimethyl propargylmalonate；dimethylpropargylmalonate sodium；dimethyl propargylmalonate
• CAS: 107201-05-8
• 化学式: C₈H₉NaO₄
• 分子量: 192.147
• InChiKey: PEPXFEBSIHZXHX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  36.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  dimethyl 1-sodium-1-propargylmalonate 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 1,1'-双(二苯基膦)二茂铁 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 Dimethyl 6-(3-hydroxypropyl)-4-methyl-1,3-dihydroindene-2,2-dicarboxylate
  参考文献：
  名称：

  Iridium Complex-Catalyzed [2+2+2] Cycloaddition of α,ω-Diynes with Monoynes and Monoenes

  摘要：

  [Ir(cod)Cl](2)/DPPE was found to be a new catalyst for the cycloaddition of alpha,omega-diynes with monoynes to give polysubstituted benzene derivatives in high yields. Internal monoynes as well as terminal monoynes could be used. The reaction tolerates a broad range of functional groups such as alcohol, amine, alkene, ether, halogen, and nitrile. The reaction of 1,6-octadiyne derivatives with 1-alkynes gives ortho products and meta products. The regioselectivity could be controlled by the choice of ligand. The reaction with DPPE was meta selective, with meta selectivity of up to 82%. The reaction with DPPF was ortho selective, with ortho selectivity of up to 88%. We propose a mechanism to account for this regioselective cycloaddition. [Ir(cod)Cl-2]2/DPPE also catalyzed the cycloaddition of alpha-omega-diynes with 2,5-dihydrofuran to give bicyclic cyclohexadiene derivatives. The reaction with 2,3-dihydrofuran and n-butyl vinyl ether gave benzene derivatives instead of cyclohexadiene derivatives. We also propose a mechanism to account for this novel aromatization that includes cleavage of the C-O bond.

  DOI：

  10.1021/jo051874c

文献信息

• Nucleophilic substitutions of 1-alkenylcyclopropyl esters and 1-alkynylcyclopropyl chlorides catalyzed by palladium(0)
  作者：Andreas Stolle、Jean Ollivier、Pier Paolo Piras、Jacques Salaun、Armin De Meijere

  DOI：10.1021/ja00037a006

  日期：1992.5

  dimethylallyl acetates 19 and 22, respectively. Use of chiral phosphines as ligands in the palladium catalyst can provide optically active methylenecyclopropane derivatives. With phenyl-, methyl-, and even n-butylzinc chloride as nucleophiles, the reaction apparently proceeds with initial transfer of the organic residue to palladium, followed by reductive elimination entailing tertiary substitution on the cyclopropane

  1-乙烯基环丙基磺酸盐 2e,f 和 2-环亚丙基乙酯 10b,c 很容易从环丙酮半缩醛 1 中获得，通过不对称的 1,1-二亚甲基-pi}-烯丙基络合物 23 进行区域选择性 Pd(0) 催化的亲核取代。稳定的阴离子（丙二酸酯的烯醇化物、β}-二羰基化合物、β}-磺酰酯和席夫碱以及乙酸根阴离子、磺酰胺阴离子等），亲核取代仅发生在末端乙烯基位置，提供环亚丙基乙基衍生物作为具有高合成潜力的基石。竞争实验表明，甲苯磺酸 1-乙烯基环丙基酯 (2e) 和环亚丙基乙酸乙酯 (10b) 分别比乙酸二甲基烯丙酯 19 和 22 更具反应性。在钯催化剂中使用手性膦作为配体可以提供旋光亚甲基环丙烷衍生物。使用苯基氯化锌、甲基氯化锌甚至正丁基氯化锌作为亲核试剂时，反应显然会进行，首先将有机残基转移到钯上，然后进行还原消除，仅在环丙烷环上进行三级取代；用叠氮化物和双(三甲基甲硅烷基)酰胺得到相同类型的产
• A Synthesis of β-necrodol via a palladium catalyzed reductive enyne cyclization
  作者：Barry M. Trost、Rebecca Braslau

  DOI：10.1016/s0040-4039(00)80263-4

  日期：1988.1

  The Pd catalyzed reductive enyne cyclization provides an approach to control 1,3- diastereoselectivity and thereby provides a five step synthesis of β-necrodol, a key substituent of the defensive secretion of the red-lined carrion beetle.

  Pd催化的还原性烯炔环化提供了一种控制1,3-非对映选择性的方法，从而提供了五步合成β-necrodol（β-necrodol）的方法，β-necrodol是红线腐肉甲虫防御性分泌物的关键取代基。
• Prins Cyclizations in Au-Catalyzed Reactions of Enynes
  作者：Eloísa Jiménez-Núñez、Christelle K. Claverie、Cristina Nieto-Oberhuber、Antonio M. Echavarren

  DOI：10.1002/anie.200601575

  日期：2006.8.18
• Regio- and Diastereoselective Tandem Rhodium-Catalyzed Allylic Alkylation/Pauson−Khand Annulation Reactions
  作者：P. Andrew Evans、John. E. Robinson

  DOI：10.1021/ja015531h

  日期：2001.5.1
• Braese, Stefan; Schoemenauer, Sten; McGaffin, Gregory, Chemistry - A European Journal, 1996, vol. 2, # 5, p. 545 - 555
  作者：Braese, Stefan、Schoemenauer, Sten、McGaffin, Gregory、Stolle, Andreas、Meijere, Armin de

  DOI：——

  日期：——