1-cyano-1-methoxycarbonyl-2-methylene cyclopentane | 146445-29-6

• 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: 1-cyano-1-methoxycarbonyl-2-methylene cyclopentane
• 英文别名: Methyl 1-cyano-2-methylidenecyclopentane-1-carboxylate
• CAS: 146445-29-6
• 化学式: C₉H₁₁NO₂
• 分子量: 165.192
• InChiKey: HVBFKRXIGGJQMR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-氰基庚-6-炔酸甲酯 在 [Cu(phen)(PPh₃)2]NO₃ 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.33h， 以92%的产率得到1-cyano-1-methoxycarbonyl-2-methylene cyclopentane
  参考文献：
  名称：

  高效且通用的微波辅助末端和内部炔烃的铜催化的对苯二酚系留在各种嗜碳亲核试剂上

  摘要：

  本文描述了带有稳定碳亲核试剂的炔烃的高效微波辅助的Conia-ene反应。由市售铜催化剂催化的反应在中性条件下进行，并且通常甚至适用于反应性较低的亲核试剂，如丙二酸酯，氰基乙酸酯和磺酰乙酸酯衍生物。这种铜介导的环异构化也适用于内部未活化的炔烃，仅导致相应的具有E烯烃化学性质的五元产物。

  DOI：

  10.1002/adsc.201000351

文献信息

• Synthesis of ethynylidene cyclopentanes by a cyclisation catalyzed by the simultaneous presence of palladium (0) and copper (I)
  作者：Didier Bouyssi、Geneviève Balme、Jacques Gore

  DOI：10.1016/0040-4039(91)80215-r

  日期：1991.11

  Ethynylidene cyclopentanes can be formed in 35–71% yield from the reaction of the enolates of compounds such as δ-acetylenic malonates with 1-halogeno-1-alkynes. This reaction requires catalysis by both palladium (0) and copper (I) species.

  乙炔基丙二酸酯等化合物的烯醇化物与1-卤代-1-炔烃的反应可形成亚乙基环戊烷，产率为35-71％。该反应需要钯（0）和铜（I）物种的催化。
• 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.
• Intramolecular carbocupration reaction of unactivated alkynes bearing a stabilized nucleophile: Application to the synthesis of iridoid monoterpenes
  作者：Didier Bouyssi、Nuno Monteiro、Geneviève Balme

  DOI：10.1016/s0040-4039(98)02630-6

  日期：1999.2

  The copper-promoted cycloisomerization of unsaturated alkynes bearing a stabilized nucleophile is described, providing a novel synthesis of various iridoid monoterpenes. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Alkaline metallic reagent-catalyzed hydrocarbocyclization reaction ofvarious active methine compounds having an unactivated 4-alkynyl or allenyl group
  作者：Osamu Kitagawa、Takashi Suzuki、Hiroki Fujiwara、Masao Fujita、Takeo Taguchi

  DOI：10.1016/s0040-4039(99)00797-2

  日期：1999.6

  On using a catalytic amount of NaH or n-BuLi, hydrocarbocyclization;reaction of various active methine compounds having an unactivated 4-pentynyl or 3,4-pentadienyl group proceeded through proton transfer mechanism to give methylenecyclopentane derivatives in good yields. (C) 1999 Elsevier Science Ltd. All rights reserved.
• An Efficient and General Microwave-Assisted Copper-Catalyzed Conia-Ene Reaction of Terminal and Internal Alkynes Tethered to a Wide Variety of Carbonucleophiles
  作者：Sonia Montel、Didier Bouyssi、Geneviève Balme

  DOI：10.1002/adsc.201000351

  日期：2010.9.10

  This paper describes a highly efficient, microwave‐assisted, Conia‐ene reaction of alkynes bearing a stabilizing carbon nucleophile. The reaction, catalyzed by a commercially available copper catalyst, proceeds under neutral conditions and is generally applicable even to less reactive nucleophiles such as malonate, cyanoacetate, and sulfonylacetate derivatives. This copper‐mediated cycloisomerization

  本文描述了带有稳定碳亲核试剂的炔烃的高效微波辅助的Conia-ene反应。由市售铜催化剂催化的反应在中性条件下进行，并且通常甚至适用于反应性较低的亲核试剂，如丙二酸酯，氰基乙酸酯和磺酰乙酸酯衍生物。这种铜介导的环异构化也适用于内部未活化的炔烃，仅导致相应的具有E烯烃化学性质的五元产物。