Benzyl 4,4-dicyanocyclopentene-1-carboxylate | 1212022-51-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Benzyl 4,4-dicyanocyclopentene-1-carboxylate
• 英文别名: benzyl 4,4-dicyanocyclopentene-1-carboxylate
• CAS: 1212022-51-9
• 化学式: C₁₅H₁₂N₂O₂
• 分子量: 252.272
• InChiKey: HPFOSUGSXYYENA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  73.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  benzyl 2-(acetoxymethyl)buta-2,3-dienoate 、 丙二腈 在 caesium carbonate 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以78%的产率得到Benzyl 4,4-dicyanocyclopentene-1-carboxylate
  参考文献：
  名称：

  具有3,3'-Bisoxindoles的介电烯基酮启用[4 + 2]环空：两个连续的第四季立体异构中心的对映选择性产生。

  摘要：

  我们在膦介导的反应中引入了一种烯丙基酮作为介电C4合成子。膦活化后产生的高级中间体的高度亲电子性使3,3'-双-吲哚类化合物在高对映选择性[4 + 2]环空中作为两碳反应伙伴得以利用，从而可以轻松地生成包含两个相邻的第四纪立体成因中心。[4 + 2]环化产物的合成操作导致（-）-叶硫氨酸的简明全合成。

  DOI：

  10.1021/acscatal.0c05225

文献信息

• Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β′-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine
  作者：Yiting Gu、Pengfei Hu、Chunjie Ni、Xiaofeng Tong

  DOI：10.1021/jacs.5b03273

  日期：2015.5.20

  Two classes of phosphine-catalyzed addition/cycloaddition domino reactions of beta'-acetoxy allenoate 1 have been developed. The reaction of 1 with 2-acyl-3-methyl-acrylonitrile 2 readily occurs to give 2-oxabicyclo[3.3.1]nonane 3, furnishing the beta'-addition/[4 + 4] cycloaddition domino sequence. In this sequence, beta'C of allenoate 1 is an electrophilic center, and its beta'C and gamma C serve as a 1,4-dipole. When the other reaction partner is switched to 2-acyl-3-(2-pyrrole)-acrylonitrile 8, a gamma-addition/[3 + 2] cycloaddition domino reaction is instead observed, in which allenoate 1 exhibits dual electrophilic reactivity of gamma C and 1,3-dipole chemical behavior of beta C and beta'C. Furthermore, both of these two asymmetric variants have also been achieved with up to 93% ee. The domino reactions presented in this report are valuable for highly stereoselective construction of complex structures under mild reaction conditions.
• Zhang, Qiongmei; Yang, Lei; Tong, Xiaofeng, Journal of the American Chemical Society, 2010, vol. 132, p. 2550 - 2551
  作者：Zhang, Qiongmei、Yang, Lei、Tong, Xiaofeng

  DOI：——

  日期：——
• Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3’-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers
  作者：Xiaodong Tang、Chuan Xiang Alvin Tan、Wai-Lun Chan、Fuhao Zhang、Wenrui Zheng、Yixin Lu

  DOI：10.1021/acscatal.0c05225

  日期：2021.2.5

  intermediates created upon phosphine activation empowered the utilization of 3,3′-bis-oxindoles as a two-carbon reaction partner in a highly enantioselective [4 + 2] annulation, allowing for facile creation of spirocyclic bisindoline structures containing two contiguous quaternary stereogenic centers. Synthetic manipulations of the [4 + 2] annulation product led to concise total synthesis of (−)-folicanthine

  我们在膦介导的反应中引入了一种烯丙基酮作为介电C4合成子。膦活化后产生的高级中间体的高度亲电子性使3,3'-双-吲哚类化合物在高对映选择性[4 + 2]环空中作为两碳反应伙伴得以利用，从而可以轻松地生成包含两个相邻的第四纪立体成因中心。[4 + 2]环化产物的合成操作导致（-）-叶硫氨酸的简明全合成。