ethyl α-diazo-2-(ethoxycarbonyl)cyclopent-1-ene-1-acetate | 1443778-57-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: ethyl α-diazo-2-(ethoxycarbonyl)cyclopent-1-ene-1-acetate
• 英文别名: (E)-[(2E)-2-(1-diazonio-2-ethoxy-2-oxoethylidene)cyclopentylidene]-ethoxymethanolate
• CAS: 1443778-57-1
• 化学式: C₁₂H₁₆N₂O₄
• 分子量: 252.27
• InChiKey: NOISVBIFZFAQPF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl α-diazo-2-(ethoxycarbonyl)cyclopent-1-ene-1-acetate 在 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 36.0h， 以89%的产率得到6-ethoxy-3-ethoxycarbonyl-4,5-propanopyridazine
  参考文献：
  名称：

  重氮哒嗪合成策略：重氮前体构型对工艺的关键影响

  摘要：

  具有乙烯基键上官能团的顺式立体化学的乙烯基重氮羰基化合物的磷酸根可通过diaza -Wittig工艺轻松生成哒嗪，而在相似的反应条件下，具有反式构型的对应物则保持完整。当UV照射反通过串联-phosphazenes配料哒嗪的反式-到-顺式异构化，接着分子内环化。在高温下反-（三苯基）磷腈分解生成最初的乙烯基重氮化合物，该化合物高产率生产吡唑。在M06-2X / 6-31G（d）理论水平上通过DFT计算对diaza-Wittig过程机理的第一个理论研究表明，对于顺式-磷腈，快速串联[2 + 2]环加成/环消除过程低能垒比反式异构体更可取。

  DOI：

  10.1002/chem.201503448
• 作为产物：
  描述：

  ethyl 2-(2-ethoxy-2-oxoethyl)cyclopent-1-enecarboxylate 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到ethyl α-diazo-2-(ethoxycarbonyl)cyclopent-1-ene-1-acetate
  参考文献：
  名称：

  Two-Stage Synthesis of 3-(Perfluoroalkyl)-Substituted Vinyldiazocarbonyl Compounds and Their Nonfluorinated Counterparts: A Comparative Study

  摘要：

  Two approaches for the synthesis of fluorinated (F) and nonfluorinated (H) 4-(alkoxycarbonyl)-substituted cis- and trans-vinyldiazocarbonyl compounds with substituents of variable stereoelectronic nature (H, Me, Ph, CF3, OTBS) at the C-3 atom of the vinyl double bond from the relevant 1,3-dicarbonyl compounds were compared: a pathway using the Wittig reaction followed by a diazo transfer reaction was most efficient for the synthesis of the H-vinyldiazocarbonyl compounds (total yields of up to 60%), while the yields of their F-analogues under similar conditions did not exceed 16-37%. An approach via diazo transfer followed by the Wittig reaction, in contrast, is more effective for the preparation of F-vinyldiazocarbonyl compounds (total yields 37-69%). The configuration of the resulting F-and H-vinyldiazocarbonyl compounds is evidently controlled by the steric bulk of the substituent at the C-3 atom of the vinyl double bond and, in addition, depends on the specific synthetic pathway.

  DOI：

  10.1055/s-0032-1318309

文献信息

• Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: experimental and computational study
  作者：Murat B. Supurgibekov、David Cantillo、C. Oliver Kappe、G. K. Surya Prakash、Valerij A. Nikolaev

  DOI：10.1039/c3ob42102c

  日期：——

  Non-fluorinated vinyldiazo compounds with trans-configuration irrespective of the nature of 3-R1-substituent (R1 = H, Me, TBSO) even under ambient conditions easily cyclize to produce pyrazoles, while cis-stereoisomers undergo similar ring closure only at elevated temperatures or decompose to produce vinyloxocarbene reaction products. The 3-CF3-substituted analogues with cis- or trans-configuration do not produce pyrazoles at all, but on heating furnish only vinylcarbene derived products. DFT calculations of theoretical energy barriers adequately explain the different experimental reactivity found for stereoisomeric vinyldiazocarbonyl compounds, and a new model for their interconversion through the corresponding pyrazoles has been suggested.

  反式结构的非氟乙烯基重氮化合物，无论 3-R1 取代基（R1 = H、Me、TBSO）的性质如何，即使在环境条件下也很容易环化生成吡唑，而顺式立体异构体只有在温度升高时才会发生类似的闭环，或者分解生成乙烯基氧羰基反应产物。顺式或反式构型的 3-CF3 取代类似物根本不会产生吡唑，而是在加热时只产生乙烯基羰基衍生产物。对理论能垒的 DFT 计算充分解释了立体异构体乙烯基二氮羰基化合物的不同实验反应性，并提出了通过相应吡唑实现相互转化的新模型。