sodium dimethylpropargylmalonate | 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: sodium dimethylpropargylmalonate
• 英文别名: sodiopropargylmalonate；Sodium;dimethyl 2-prop-2-ynylpropanedioate
• CAS: 107201-05-8
• 化学式: C₈H₉O₄*Na
• 分子量: 192.147
• InChiKey: DKGURGPEIVAIGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.07
• 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：
  52.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  sodium dimethylpropargylmalonate 在 1,2-双(二苯基膦)乙烷 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ N-甲基吲哚酮 作用下， 反应 14.0h， 生成 Dimethyl 3a-methyl-5-oxospiro[1,3-dihydropentalene-4,1'-cyclopropane]-2,2-dicarboxylate
  参考文献：
  名称：

  亚甲基环丙烷终止剂在分子内Pauson-Khand反应中的优势

  摘要：

  诸如2的6-环丙叉基-1-己炔，例如通过钯（0）催化的1-乙烯基环丙基磺酸盐1的取代而制备的，其分子内的Pauson-Khand反应既有效地又是区域选择性的。

  DOI：

  10.1016/s0040-4039(00)73224-2

文献信息

• Syntheses of the picrotoxane skeleton via the palladium (II) - catalyzed carbacyclization reaction
  作者：Barry M Trost、David J Jebaratnam

  DOI：10.1016/s0040-4039(00)95372-3

  日期：1987.1

  The ability of the palladium (+2)-catalyzed intramolecular carbametalation to form quaternary and vicinal quaternary centers in anti-Markovnikov fashion was demonstrated by the syntheses of the picrotoxane skeleton.

  吡咯烷烷骨架的合成证明了钯（+2）催化的分子内碳金属化反应以反马尔科夫尼科夫形式形成季和邻季碳中心的能力。
• Palladium−Cobalt-Mediated Double Annulation Process:  A New Strategy to Chiral and Polysubstituted Bis-Cyclopentanoids on Carbohydrate Precursors
  作者：Noshena Naz、Taleb H. Al-Tel、Yousef Al-Abed, and、Wolfgang Voelter、Robert Ficker、Wolfgang Hiller

  DOI：10.1021/jo951298s

  日期：1996.1.1

  The iodohydrins 2, 4, and 5 mere prepared by the ring opening of benzyl 2-O-p-tosyl-3,4-anhydro-beta-L-arabinopyranoside (1) or benzyl 2,3-anhydro-4-O-acetyl-alpha-D-ribopyranoside (3), respectively, using sodium acetate, sodium iodide, and acetic acid in acetone which on treatment with POCl3 in pyridine yielded the unsaturated sugars 6 and 7. After deacetylation of 7 with MeOH/H2O/Et(3)N (3:2:1) and treatment of 8 with tosyl chloride/pyridine at 50 degrees C 9 was obtained. The reaction of benzyl 2-O-p-tosyl-3,4-dideoxy-alpha-D-glycero-pent-3-eopyranoside (6) and benzyl 2,3,4-trideoxy-4-chloro-beta-L-glycero-pent-2-enopyranoside (9) with the sodium enolate of dimethyl propargylmalonate in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0) afforded the branched-chain sugars 10 and 11. The isomer 10 was obtained as a minor product from 6 with retention of configuration around C-2, and the major isomer 11 as a result of allylic rearrangement in a ratio of 1:9. On the other hand, compound 9 afforded 10 as a major product and its regioisomer 11 as a minor product in a ratio of 8:2; formation of the above mentioned isomeric mixture involves cis and trans diastereomeric intermediates during the reaction. Treatment of these precursors with Co-2(CO)(8) in benzene followed by oxidative decomplexation with DMSO yielded in a stereoselective manner the polysubstituted bis-cyclopentanoids 12 and 13. The stereochemistry of 13 was assigned with the help of X-ray analysis. Attempts were made to prepare the tetracyclic systems 15 and 17 using 12 and 13 with 3-acetoxy-2-[(trimethylsilyl)methyl]-1-propene (14); however, the alkylation products 16 and 18 were obtained.
• The virtue of methylenecyclopropane terminators in intramolecular Pauson-Khand reactions
  作者：Andreas Stolle、Heike Becker、Jacques Salaün、Armin de Meijere

  DOI：10.1016/s0040-4039(00)73224-2

  日期：1994.5

  6-Cyclopropylidene-1-hexynes like 2, e. g. prepared via palladium(0)-catalyzed substitution of 1-ethenyl cyclopropyl sulfonates 1, undergo an intramolecular Pauson-Khand reaction both efficiently and regioselectively.

  诸如2的6-环丙叉基-1-己炔，例如通过钯（0）催化的1-乙烯基环丙基磺酸盐1的取代而制备的，其分子内的Pauson-Khand反应既有效地又是区域选择性的。