(Z)-(R^*,S^*)-6-<9-Methyl-8-(4-methyl-5-methoxy-2-oxazolyl)-1,4-dithiaspiro<4.4>non-8-en-7-yl>-1-methoxy-4-<(tert-butyldimethylsilyl)oxy>hept-4-en-2-yne | 143817-55-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (Z)-(R^*,S^*)-6-<9-Methyl-8-(4-methyl-5-methoxy-2-oxazolyl)-1,4-dithiaspiro<4.4>non-8-en-7-yl>-1-methoxy-4-<(tert-butyldimethylsilyl)oxy>hept-4-en-2-yne
• 英文别名: tert-butyl-[(Z,6R)-1-methoxy-6-[(7R)-8-(5-methoxy-4-methyl-1,3-oxazol-2-yl)-9-methyl-1,4-dithiaspiro[4.4]non-8-en-7-yl]hept-4-en-2-yn-4-yl]oxy-dimethylsilane
• CAS: 143817-55-4
• 化学式: C₂₇H₄₁NO₄S₂Si
• 分子量: 535.844
• InChiKey: OTZBDIRQHHTADF-GRGVEOHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.15
• 重原子数：
  35
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (Z)-(R^*,S^*)-6-<9-Methyl-8-(4-methyl-5-methoxy-2-oxazolyl)-1,4-dithiaspiro<4.4>non-8-en-7-yl>-1-methoxy-4-<(tert-butyldimethylsilyl)oxy>hept-4-en-2-yne 在 sodium tetrahydroborate 、 四丁基氟化铵 、 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 5.33h， 生成
  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-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 tert-Butyldimethylsilyl ether 以 苯 为溶剂， 反应 0.5h， 以76%的产率得到(Z)-(R^*,S^*)-6-<9-Methyl-8-(4-methyl-5-methoxy-2-oxazolyl)-1,4-dithiaspiro<4.4>non-8-en-7-yl>-1-methoxy-4-<(tert-butyldimethylsilyl)oxy>hept-4-en-2-yne
  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.