2,3-dimethoxy-6-methylenespiro[4.4]non-2-en-1-one | 220485-21-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: 2,3-dimethoxy-6-methylenespiro[4.4]non-2-en-1-one
• 英文别名: 2,3-Dimethoxy-9-methylidenespiro[4.4]non-2-en-4-one；2,3-dimethoxy-9-methylidenespiro[4.4]non-2-en-4-one
• CAS: 220485-21-2
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: CVBOUNVDMBOWRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,3-dimethoxy-6-methylenespiro[4.4]non-2-en-1-one 在 四氧化锇 、 selenium(IV) oxide 、 N-甲基吲哚酮 、 水 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 叔丁醇 为溶剂， 生成 (5R*,6R*)-6-hydroxy-6-(hydroxymethyl)-2,3-dimethoxyspiro[4.4]non-2-ene-1,7-dione
  参考文献：
  名称：

  α-Carbonyl radical cyclization approach toward spiro[4.4]nonene: total synthesis of dimethyl gloiosiphone A

  摘要：

  通过δ-羰基自由基螺环化反应，实现了二甲基球形酮 A 2 的全合成。

  DOI：

  10.1039/a808455f
• 作为产物：
  描述：

  5-碘-1-戊炔 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 66.34h， 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

文献信息

• α-Carbonyl radical cyclization approach toward spiro[4.4]nonene: total synthesis of dimethyl gloiosiphone A
  作者：Chin-Kang Sha、Wen-Yueh Ho

  DOI：10.1039/a808455f

  日期：——

  The total synthesis of dimethyl gloiosiphone A 2 was achieved via an α-carbonyl radical spirocyclization.

  通过δ-羰基自由基螺环化反应，实现了二甲基球形酮 A 2 的全合成。
• Synthesis of Dimethyl Gloiosiphone A by Way of Palladium-Catalyzed Domino Cyclization
  作者：Takayuki Doi、Yusuke Iijima、Masaru Takasaki、Takashi Takahashi

  DOI：10.1021/jo062546v

  日期：2007.5.1

  The synthesis of a spiro[4.4]nonane skeleton by the palladium-catalyzed domino cyclization of a linear 7-methylene-2,10-undecadienyl acetate is described. The π-allylpalladium intermediate underwent intramolecular alkene insertion with high intraannular diastereoselectivity, followed by intramolecular Heck-type cyclization, leading to a spiro[4.4]nonane system. Oxidation of the allylic ether moiety

  描述了通过钯催化线性的7-亚甲基-2,10-十一碳二烯基乙酸酯的多米诺环化反应来合成螺[4.4]壬烷骨架。π-烯丙基钯中间体经历了高环内非对映选择性的分子内烯烃插入，随后进行了分子内Heck型环化，形成了螺[4.4]壬烷体系。烯丙基醚部分和乙烯基的变换到的氧化外-亚甲基单元提供3，这是公知的合成中间体二甲gloiosiphone A（的2）。
• Total Synthesis of Dimethyl Glolosiphone A<i>via</i>α-Carbonyl Radical Spiro-Cyclization
  作者：Chin-Kang Sha、Wen-Yueh Ho

  DOI：10.1002/jccs.199900064

  日期：1999.6

  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).