Dimethyl 6-methyl-1,4-dioxaspiro<4.4>non-7-ene-6,7-dicarboxylate | 143817-37-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Dimethyl 6-methyl-1,4-dioxaspiro<4.4>non-7-ene-6,7-dicarboxylate
• 英文别名: Dimethyl 9-methyl-1,4-dioxaspiro[4.4]non-7-ene-8,9-dicarboxylate
• CAS: 143817-37-2
• 化学式: C₁₂H₁₆O₆
• 分子量: 256.255
• InChiKey: IIPBMWVQUXEKDB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Dimethyl 6-methyl-1,4-dioxaspiro<4.4>non-7-ene-6,7-dicarboxylate 在 吡啶 、 sodium hydroxide 、 草酰氯 、 磷酸三丁酯 、 phosphorus pentoxide 、 碳酸氢钠 、 potassium carbonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 6.0h， 生成 Methyl 6-methyl-7-(4-methyl-5-methoxy-2-oxazolyl)-1,4-dioxaspiro<4.4>non-7-ene-6-carboxylate
  参考文献：
  名称：

  Bis-heteroannulation. 16. A synthetic approach to geigerin

  摘要：

  Furano alcohol 5, the key intermediate in our proposed synthesis of the guaianolide sesquiterpene geigerin (1), was prepared by a novel sequence of reactions which includes a chemoselective oxy-Cope transformation of enynols of general structure 42. Although 42 itself underwent oxy-Cope reaction with exclusive triple-bond participation, the corresponding tert-butyldimethylsilyl ether 46 gave the desired vinyl silyloxy Cope product 48 with 100% selectivity. The conversion of acetylenic oxazole 48 to 5 was then effected by a highly efficient (Diels-Alder)-(retro-Diels-Alder) transformation to generate the guaiane ketone 20, followed by hydride reduction.

  DOI：

  10.1021/jo00049a044
• 作为产物：
  描述：

  2-methyl-2,3-bis(methoxycarbonyl)cyclopentanone 在 DOWEX 50W-X₄ 、 双氧水 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 乙酸乙酯 、 苯 为溶剂， 反应 72.0h， 生成 Dimethyl 6-methyl-1,4-dioxaspiro<4.4>non-7-ene-6,7-dicarboxylate
  参考文献：
  名称：

  Bis-heteroannulation. 16. A synthetic approach to geigerin

  摘要：

  Furano alcohol 5, the key intermediate in our proposed synthesis of the guaianolide sesquiterpene geigerin (1), was prepared by a novel sequence of reactions which includes a chemoselective oxy-Cope transformation of enynols of general structure 42. Although 42 itself underwent oxy-Cope reaction with exclusive triple-bond participation, the corresponding tert-butyldimethylsilyl ether 46 gave the desired vinyl silyloxy Cope product 48 with 100% selectivity. The conversion of acetylenic oxazole 48 to 5 was then effected by a highly efficient (Diels-Alder)-(retro-Diels-Alder) transformation to generate the guaiane ketone 20, followed by hydride reduction.

  DOI：

  10.1021/jo00049a044

文献信息

• Bis-heteroannulation. 16. A synthetic approach to geigerin
  作者：Peter A. Jacobi、Kim M. Touchette、Harold G. Selnick

  DOI：10.1021/jo00049a044

  日期：1992.11

  Furano alcohol 5, the key intermediate in our proposed synthesis of the guaianolide sesquiterpene geigerin (1), was prepared by a novel sequence of reactions which includes a chemoselective oxy-Cope transformation of enynols of general structure 42. Although 42 itself underwent oxy-Cope reaction with exclusive triple-bond participation, the corresponding tert-butyldimethylsilyl ether 46 gave the desired vinyl silyloxy Cope product 48 with 100% selectivity. The conversion of acetylenic oxazole 48 to 5 was then effected by a highly efficient (Diels-Alder)-(retro-Diels-Alder) transformation to generate the guaiane ketone 20, followed by hydride reduction.