methyl 2-[(8'S,8'aR)-3',8'-dimethyl-4'-oxospiro[1,3-dithiolane-2,2'-1,7,8,8a-tetrahydroazulene]-5'-yl]prop-2-enoate | 143817-31-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl 2-[(8'S,8'aR)-3',8'-dimethyl-4'-oxospiro[1,3-dithiolane-2,2'-1,7,8,8a-tetrahydroazulene]-5'-yl]prop-2-enoate
• CAS: 143817-31-6
• 化学式: C₁₈H₂₂O₃S₂
• 分子量: 350.503
• InChiKey: YPJGKQJVZQDFKT-IINYFYTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  94
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-[(8'S,8'aR)-3',8'-dimethyl-4'-oxospiro[1,3-dithiolane-2,2'-1,7,8,8a-tetrahydroazulene]-5'-yl]prop-2-enoate 生成 、 (2E)-2-[(8'S,8'aR)-3',8'-dimethyl-4'-oxospiro[1,3-dithiolane-2,2'-8,8a-dihydro-1H-azulene]-5'-ylidene]propanoic acid
  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：

  (R^*,S^*)-6-<9-Methyl-8-(4-methyl-5-methoxy-2-oxazolyl)-1,4-dithiaspiro<4.4>non-8-en-7-yl>-1-methoxyhept-2-yn-4-one 在 吡啶 、 sodium tetrahydroborate 、 硫酸 、 碳酸氢钠 、 对苯二酚 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 28.0h， 生成 methyl 2-[(8'S,8'aR)-3',8'-dimethyl-4'-oxospiro[1,3-dithiolane-2,2'-1,7,8,8a-tetrahydroazulene]-5'-yl]prop-2-enoate
  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.