(2E,6Z,10E)-14,15-epoxy-3,11,15-trimethyl-7-<(trimethylsilyl)methyl>-2,6,10-hexadecatrien-1-ol | 142793-50-8

• 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: (2E,6Z,10E)-14,15-epoxy-3,11,15-trimethyl-7-<(trimethylsilyl)methyl>-2,6,10-hexadecatrien-1-ol
• 英文别名: (2E,6Z,10E)-14,15-epoxy-3,11,15-trimethyl-7-[(trimethylsilyl)methyl]-2,6,10-hexadecatrien-1-ol；(2E,6Z,10E)-13-(3,3-dimethyloxiran-2-yl)-3,11-dimethyl-7-(trimethylsilylmethyl)trideca-2,6,10-trien-1-ol
• CAS: 142793-50-8
• 化学式: C₂₃H₄₂O₂Si
• 分子量: 378.671
• InChiKey: QCVFZGAPRKLTCW-NKFREGGASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.65
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (2E,6Z,10E)-14,15-epoxy-3,11,15-trimethyl-7-<(trimethylsilyl)methyl>-2,6,10-hexadecatrien-1-ol 在 吡啶 作用下， 反应 10.0h， 以99%的产率得到(2E,6Z,10E)-14,15-epoxy-3,11,15-trimethyl-7-<(trimethylsilyl)methyl>-2,6,10-hexadecatrienyl acetate
  参考文献：
  名称：

  Total synthesis of (+)-9,10-syn- and (+)-9,10-anti-copalol via epoxy trienylsilane cyclizations.

  摘要：

  Total syntheses of (+)-9,10-syn-copalol (5), the pyrophosphate ester of which is a likely intermediate in the biosynthesis of 9,10-syn diterpenes, and its 9,10-anti isomer 39 are reported. Lithiation of (-)-(6R)-6,7-epoxygeranyl p-tolylsulfone (-)-19 or (+/-)-19 followed by alkylation with (E,Z)- and (E,E)-8-bromo-9-(trimethylsilyl)geranyl benzyl ethers (15a and 15b) and selective reductive cleavage of the toluenesulfonyl and benzyl groups afforded (2E,6E,10E,14R)- and (2E,6Z,10E,14R)-14,15-epoxy-19-(trimethylsilyl)geranylgeraniols ((-)-24a and (+/-)-26a). Lewis acid treatment of the benzoate and/or acetates of (-)-24a and (+/-)-26a effected efficient but almost stereorandom bicyclizations to 9,10-syn- and 9,10-anti-labda-8(17),13(E)-diene-3-beta,15-diol esters (27a,b and 28a,b) which were converted to (+)-9,10-syn- and (+)-9,10-anti-copalol.

  DOI：

  10.1021/jo00043a014
• 作为产物：
  描述：

  3-trimethylsilyl-2-diethylphosphonopropionic acid ethyl ester 在 lithium aluminium tetrahydride 、 正丁基锂 、 三氯化铝 、 18-冠醚-6 、 lithium 、 potassium hydride 、 乙胺 、 三乙胺 、 lithium bromide 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.5h， 生成 (2E,6Z,10E)-14,15-epoxy-3,11,15-trimethyl-7-<(trimethylsilyl)methyl>-2,6,10-hexadecatrien-1-ol
  参考文献：
  名称：

  Total synthesis of (+)-9,10-syn- and (+)-9,10-anti-copalol via epoxy trienylsilane cyclizations.

  摘要：

  Total syntheses of (+)-9,10-syn-copalol (5), the pyrophosphate ester of which is a likely intermediate in the biosynthesis of 9,10-syn diterpenes, and its 9,10-anti isomer 39 are reported. Lithiation of (-)-(6R)-6,7-epoxygeranyl p-tolylsulfone (-)-19 or (+/-)-19 followed by alkylation with (E,Z)- and (E,E)-8-bromo-9-(trimethylsilyl)geranyl benzyl ethers (15a and 15b) and selective reductive cleavage of the toluenesulfonyl and benzyl groups afforded (2E,6E,10E,14R)- and (2E,6Z,10E,14R)-14,15-epoxy-19-(trimethylsilyl)geranylgeraniols ((-)-24a and (+/-)-26a). Lewis acid treatment of the benzoate and/or acetates of (-)-24a and (+/-)-26a effected efficient but almost stereorandom bicyclizations to 9,10-syn- and 9,10-anti-labda-8(17),13(E)-diene-3-beta,15-diol esters (27a,b and 28a,b) which were converted to (+)-9,10-syn- and (+)-9,10-anti-copalol.

  DOI：

  10.1021/jo00043a014

文献信息

• Total synthesis of (+)-9,10-syn- and (+)-9,10-anti-copalol via epoxy trienylsilane cyclizations.
  作者：Nathan K. N. Yee、Robert M. Coates

  DOI：10.1021/jo00043a014

  日期：1992.8

  Total syntheses of (+)-9,10-syn-copalol (5), the pyrophosphate ester of which is a likely intermediate in the biosynthesis of 9,10-syn diterpenes, and its 9,10-anti isomer 39 are reported. Lithiation of (-)-(6R)-6,7-epoxygeranyl p-tolylsulfone (-)-19 or (+/-)-19 followed by alkylation with (E,Z)- and (E,E)-8-bromo-9-(trimethylsilyl)geranyl benzyl ethers (15a and 15b) and selective reductive cleavage of the toluenesulfonyl and benzyl groups afforded (2E,6E,10E,14R)- and (2E,6Z,10E,14R)-14,15-epoxy-19-(trimethylsilyl)geranylgeraniols ((-)-24a and (+/-)-26a). Lewis acid treatment of the benzoate and/or acetates of (-)-24a and (+/-)-26a effected efficient but almost stereorandom bicyclizations to 9,10-syn- and 9,10-anti-labda-8(17),13(E)-diene-3-beta,15-diol esters (27a,b and 28a,b) which were converted to (+)-9,10-syn- and (+)-9,10-anti-copalol.