(1α,3β,8aβ,10aα)-1,2,3,8,8a,9,10,10a-octahydro-8a,10a-dimethyl-1-(1-methylethyl)-3-triethylsilyloxy-5-triethylsilyloxymethyl-benz[f]azulen-6(7H)-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1α,3β,8aβ,10aα)-1,2,3,8,8a,9,10,10a-octahydro-8a,10a-dimethyl-1-(1-methylethyl)-3-triethylsilyloxy-5-triethylsilyloxymethyl-benz[f]azulen-6(7H)-one
• 英文别名: (1S,3R,3aR,5aR)-3a,5a-dimethyl-3-propan-2-yl-1-triethylsilyloxy-9-(triethylsilyloxymethyl)-2,3,4,5,6,7-hexahydro-1H-benzo[f]azulen-8-one
• 化学式: C₃₂H₅₈O₃Si₂
• 分子量: 546.982
• InChiKey: LAXQZNXRGCRELD-SSHYCOHZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.47
• 重原子数：
  37
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1α,3β,8aβ,10aα)-1,2,3,8,8a,9,10,10a-octahydro-8a,10a-dimethyl-1-(1-methylethyl)-3-triethylsilyloxy-5-triethylsilyloxymethyl-benz[f]azulen-6(7H)-one 在 溶剂黄146 、 lithium tri-t-butoxyaluminum hydride 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 (1α,3β,6α,8aβ,10aα)-1,2,3,6,7,8,8a,9,10,10a-decahydro-5-hydroxymethyl-8a,10a-dimethyl-1-(1-methylethyl)-3,6-benz[f]azulenediol
  参考文献：
  名称：

  Formal Synthesis of (±)-Guanacastepene A

  摘要：

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.

  DOI：

  10.1021/jo026702j
• 作为产物：
  描述：

  5-(tetrahydro-2H-pyran-2-yloxy)-2-pentyn-1-ol 在 吡啶 、 N,N-二甲基丙烯基脲 、 pyr*(HF)x 、 sodium methylate 、 三乙胺 、 sodium iodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 4.5h， 生成 (1α,3β,8aβ,10aα)-1,2,3,8,8a,9,10,10a-octahydro-8a,10a-dimethyl-1-(1-methylethyl)-3-triethylsilyloxy-5-triethylsilyloxymethyl-benz[f]azulen-6(7H)-one
  参考文献：
  名称：

  Formal Synthesis of (±)-Guanacastepene A

  摘要：

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.

  DOI：

  10.1021/jo026702j

文献信息

• Formal Synthesis of (±)-Guanacastepene A
  作者：Bo Shi、Natalie A. Hawryluk、Barry B. Snider

  DOI：10.1021/jo026702j

  日期：2003.2.1

  A 17 step synthesis of 55, a late intermediate in Danishefsky's guanacastepene A synthesis, has been completed in 4% overall yield. Key features include the use of vinylmagnesium bromide in the Pd-catalyzed coupling with triflate 13 to give triene 16 without the formation of Heck products, a novel extension of the Stork-Jung vinylsilane Robinson annulation that provides tricyclic 2-hydroxymethylcyclohexenone 42 from 23b in four steps and 51% yield, the ability to obtain almost exclusively alpha'-alkylation of 35ba by the proper choice of protecting groups, and the ability to obtain the desired -alcohol selectively by reduction of keto alcohol 42 rather than keto ester 53.