2--2-ethoxycarbonyl-cyclopentanon | 10555-54-1

• 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: 2--2-ethoxycarbonyl-cyclopentanon
• 英文别名: 2-(Pentin-4-yl-1)-2-ethoxycarbonyl-cyclopentanon；Ethyl 2-oxo-1-pent-4-ynylcyclopentane-1-carboxylate
• CAS: 10555-54-1
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: XDJBGHMRXLZYNF-UHFFFAOYSA-N

物化性质

• 沸点：
  94-96 °C(Press: 0.3 Torr)
• 密度：
  1.065±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2--2-ethoxycarbonyl-cyclopentanon 在 sodium methylate 、 六正丁基二锡 、 sodium hydride 、 二甲基亚砜 、 间氯过氧苯甲酸 、 六甲基二硅氮烷 、 sodium iodide 、 lithium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 49.84h， 生成 2,3-dimethoxy-6-methylenespiro[4.4]non-2-en-1-one
  参考文献：
  名称：

  Total Synthesis of Dimethyl Glolosiphone Aviaα-Carbonyl Radical Spiro-Cyclization

  摘要：

  AbstractA general approach toward spiro[4.4]nonane structure based on the α‐carbonyl radical cyclization has been developed. Efficient total synthesis of dimethyl gloiosiphone A (2) was achieved. Thus, alkylation of the anion of dimethylhydrazone of cyclopentanone with 5‐iodopent‐1‐yne followed by hydrolysis gave ketone 4. Iodination of 4 via its TMS‐enol ether yielded iodo ketone 7. Radical spiro‐cyclization of 7 gave spiro ketone 10. Iodination of 10 afford iodo spiro ketone 23. Oxidation and iodination of 23 gave compound 24. Methylation of 24 furnished methoxy iodo enone 25. Substitution of iodide in 25 with methoxide produced dimethoxy enone 26. Allylic oxidation of 26 gave diketone 27. Treatment of 27 with OsO4 and N‐methylmorpholine N‐oxide gave dihydroxy ketone 28. Methylation of the primary alcohol group in 28 afforded dimethyl gloiosiphone A (2).

  DOI：

  10.1002/jccs.199900064
• 作为产物：
  描述：

  5-碘-1-戊炔 、 2-氧代环戊羧酸乙酯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.5h， 生成 2--2-ethoxycarbonyl-cyclopentanon
  参考文献：
  名称：

  Total Synthesis of Dimethyl Glolosiphone Aviaα-Carbonyl Radical Spiro-Cyclization

  摘要：

  AbstractA general approach toward spiro[4.4]nonane structure based on the α‐carbonyl radical cyclization has been developed. Efficient total synthesis of dimethyl gloiosiphone A (2) was achieved. Thus, alkylation of the anion of dimethylhydrazone of cyclopentanone with 5‐iodopent‐1‐yne followed by hydrolysis gave ketone 4. Iodination of 4 via its TMS‐enol ether yielded iodo ketone 7. Radical spiro‐cyclization of 7 gave spiro ketone 10. Iodination of 10 afford iodo spiro ketone 23. Oxidation and iodination of 23 gave compound 24. Methylation of 24 furnished methoxy iodo enone 25. Substitution of iodide in 25 with methoxide produced dimethoxy enone 26. Allylic oxidation of 26 gave diketone 27. Treatment of 27 with OsO4 and N‐methylmorpholine N‐oxide gave dihydroxy ketone 28. Methylation of the primary alcohol group in 28 afforded dimethyl gloiosiphone A (2).

  DOI：

  10.1002/jccs.199900064

文献信息

• A formal synthesis of ptaquilosin the aglycon of a potent bracken carcinogen ptaquiloside
  作者：Janine Cossy、Saïd Ibhi、Philippe H. Kahn、Laura Tacchini

  DOI：10.1016/0040-4039(95)01552-s

  日期：1995.10

  A formal synthesis of racemic and optically active plaquilosin has been achieved from the commercially available methyl 2-oxoycyclopentaneearboxylate.

  已从市售的2-氧代环戊烷羧酸甲酯中获得了外消旋和旋光性plaquilosin的正式合成。
• Intramolecular Schmidt Reaction of Vinyl Azides with Cyclic Ketones
  作者：Peng Chen、Chu-Han Sun、Yu Wang、Ying Xue、Chen Chen、Mei-Hua Shen、Hua-Dong Xu

  DOI：10.1021/acs.orglett.8b00395

  日期：2018.3.16

  tethered with a vinyl azide group undergo a Schmidt-hydrolysis sequence to give secondary lactams bearing a ketone side chain. Secondary lactams are obtained in a regioselective manner that is not possible in a conventional Schimdt reaction. In addition to the well-documented C-2 nucleophilicity, the N nucleophilicity of vinyl azide disclosed in this work opens a new direction for reaction invention involving

  与叠氮乙烯基连接的环状酮经过施密特水解序列，得到带有酮侧链的仲内酰胺。仲内酰胺是以区域选择性的方式获得的，这在常规的Schimdt反应中是不可能的。除了有据可证的C-2亲核性，这项工作中公开的叠氮化乙烯基的N亲核性为涉及叠氮化乙烯基的反应发明开辟了新的方向。
• A simple preparation of the hydroazulene skeleton from cyclopentanone derivatives via a free radical process
  作者：Atsushi Nishida、Yukie Ogasawara、Norio Kawahara、Mayumi Nishida

  DOI：10.1016/0040-4039(95)00502-4

  日期：1995.4

  The hydroazulene skeleton (bicyclo[5.3.0]decane) was prepared from 2-(pent-4-ynyl)cyclopentanones in a single step by a free radical reaction. The efficiency of the conversion was greatly influenced by the substituents on the cyclopentane ring and on the side chain.

  由2-（戊-4-炔基）环戊烷酮通过自由基反应一步一步制备氢杂氮烯骨架（双环[5.3.0]癸烷）。转化效率很大程度上受到环戊烷环和侧链上的取代基的影响。
• Gold-catalysed room-temperature cycloisomerisation of alkynes and unactivated enolisable ketones
  作者：Paul W. Davies、Christelle Detty-Mambo

  DOI：10.1039/c003473h

  日期：——

  The cycloisomerisation of simple keto-alkynes proceeds at room temperature under the mild conditions of gold catalysis. Bicyclic fused and spiro compounds can be obtained by overall 5-exo and 6-exo carbon–carbon bond-forming cyclisations.

  在室温下，简单的酮-炔在温和的金催化条件下发生环化异构化反应。通过5-外型和6-外型碳-碳键形成的全环化反应，可以得到双环稠合和螺环化合物。
• Mandville,G. et al., Bulletin de la Societe Chimique de France, 1973, p. 963 - 971
  作者：Mandville,G. et al.

  DOI：——

  日期：——