dimethyl 2-methylenecyclohexane-1,1-dicarboxylate | 134149-21-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 2-methylenecyclohexane-1,1-dicarboxylate
• 英文别名: 1,1-dimethoxycarbonyl-2-methylene cyclohexane；Dimethyl 2-methylidenecyclohexane-1,1-dicarboxylate
• CAS: 134149-21-6
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: VKVDJVAXOBSWLD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  dimethyl 2-(hex-5-yn-1-yl)malonate 在 四氯化锡 、 三乙胺 、 硫酸 作用下， 以 二氯甲烷 、 四氢呋喃 为溶剂， 反应 4.5h， 以91%的产率得到dimethyl 2-methylenecyclohexane-1,1-dicarboxylate
  参考文献：
  名称：

  Intramolecular Carbostannation Reaction of Active Methine Compounds with an Unactivated C−C π-Bond Mediated by SnCl₄−Et₃N

  摘要：

  In the presence of SnCl4 and Et3N, intramolecular carbostannation reaction of various active methine compounds having an unactivated alkenyl, alkynyl, or allenyl group proceeds in good yields with complete regioselectivity. The subsequent reaction of the resulting Sn intermediates with-some electrophiles provides functionalized cyclopentane and cyclohexane derivatives.

  DOI：

  10.1021/jo000784z

文献信息

• Formation de derives cyclopentaniques assistee par une espece hydrure de palladium : Aspects synthetiques et mecanisme
  作者：Nuno Monteiro、Jacques Gore、Geneviève Balme

  DOI：10.1016/s0040-4020(01)89040-2

  日期：——

  In the presence of a palladium(0) complex and potassium t-butoxide, the acetylenic compounds 2 bearing in delta a nucleophilic functionality are smoothly transformed with excellent yields, either into 2,2-difunctionalized methylene cyclopentanes or into monofunctionalized 2-methylcyclopentenes. Each of these compounds can be specifically obtained depending on the choice of the experimental conditions.A set of diverse reactions involving mainly potassium hydride as the base showed clearly that HPdOtBu is not the active catalytic species which is mainly a sigma-ethynylpalladium hydride formed by the metal insertion in the acetylenic carbon hydrogen bond.
• Carbocyclization Reaction of Active Methine Compounds with Unactivated Alkenyl or Alkynyl Groups Mediated by TiCl₄−Et₃N
  作者：Osamu Kitagawa、Takashi Suzuki、Tadashi Inoue、Yoko Watanabe、Takeo Taguchi

  DOI：10.1021/jo981603k

  日期：1998.12.1

  In the presence of TiCl4, Et3N, and I-2, iodocarbocyclization reaction of various active methine compounds having alkenyl groups gave iodocycloalkane derivatives in good yields. On the other hand, TiCl4 and Et3N promote the carbocyclization of active methine compounds with 4-alkynyl groups in the absence of I-2 to give methylenecyclopentane derivatives in good yields. This reaction proceeds with high streoselectivity through a cis-addition of trichlorotitanium enolates of active methine compounds to alkynes, and the resulting vinyltitanium intermediates can be further functionalized by the reaction with various electrophiles.
• Cyclisation of ω-unsaturated β-dicarbonylcompounds catalyzed by a palladium hydride species
  作者：Nuno Monteiro、Geneviève Balme、Jacques Gore

  DOI：10.1016/s0040-4039(00)74294-8

  日期：1991.3

  When treated with potassium t-butoxide and then with a palladium(O) complex, the title compounds 1, 2, or 9 are smoothly cyclized by an attack of the enolates onto the unsaturation assisted by a palladium (II) species of tBuO-Pd-H type. The formation of a five-membered ring is particularly favored in such a process.
• Intramolecular carbotitanation reaction of active methine compounds having an unactivated alkyne mediated by TiCl4Et3N
  作者：Osamu Kitagawa、Takashi Suzuki、Tadashi Inoue、Takeo Taguchi

  DOI：10.1016/s0040-4039(98)01579-2

  日期：1998.10

  In the presence of TiCl4 and Et3N, intramolecular carbotitanation reaction of active methine compounds having an unactivated 4-alkynyl group proceeds in a highly cis-selective manner to give methylenecyclopentane derivatives in good yields. (C) 1998 Elsevier Science Ltd. All rights reserved.