(R^*,S^*)-6-Methyl-7-(4-methyl-5-methoxy-2-oxazolyl)-α-1-(Z)-propenyl-α-(3-methoxy-1-propynyl)-1,4-dithiaspiro<4.4>non-7-ene-6-methanol | 143817-50-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (R^*,S^*)-6-Methyl-7-(4-methyl-5-methoxy-2-oxazolyl)-α-1-(Z)-propenyl-α-(3-methoxy-1-propynyl)-1,4-dithiaspiro<4.4>non-7-ene-6-methanol
• 英文别名: (Z)-7-methoxy-4-[8-(5-methoxy-4-methyl-1,3-oxazol-2-yl)-9-methyl-1,4-dithiaspiro[4.4]non-7-en-9-yl]hept-2-en-5-yn-4-ol
• CAS: 143817-50-9
• 化学式: C₂₁H₂₇NO₄S₂
• 分子量: 421.582
• InChiKey: FCAFCWGBGDBTRW-TWGQIWQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  115
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (R^*,S^*)-6-Methyl-7-(4-methyl-5-methoxy-2-oxazolyl)-α-1-(Z)-propenyl-α-(3-methoxy-1-propynyl)-1,4-dithiaspiro<4.4>non-7-ene-6-methanol 在 碳酸氢钠 作用下， 以 苯 为溶剂， 反应 1.25h， 以45%的产率得到6-<9-Methyl-8-(4-methyl-5-methoxy-2-oxazolyl)-1,4-dithiaspiro<4.4>non-8-en-7-yl>-7-methoxy-2,5-heptadien-4-one
  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：

  Dimethyl 6-methyl-1,4-dioxaspiro<4.4>non-7-ene-6,7-dicarboxylate 在 吡啶 、 sodium hydroxide 、 正丁基锂 、 草酰氯 、 磷酸三丁酯 、 三氟化硼乙醚 、 phosphorus pentoxide 、 二异丁基氢化铝 、 碳酸氢钠 、 potassium carbonate 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 26.84h， 生成 (R^*,S^*)-6-Methyl-7-(4-methyl-5-methoxy-2-oxazolyl)-α-1-(Z)-propenyl-α-(3-methoxy-1-propynyl)-1,4-dithiaspiro<4.4>non-7-ene-6-methanol
  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.