(1β,3α,3aα)-1,2,3,3a,4,5-hexahydro-3a-methyl-3-(1-methylethyl)-1-(tert-butyldimethylsilyloxy)-7(6H)-azulenone

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1β,3α,3aα)-1,2,3,3a,4,5-hexahydro-3a-methyl-3-(1-methylethyl)-1-(tert-butyldimethylsilyloxy)-7(6H)-azulenone
• 英文别名: (1R,3S,8aR)-3-[tert-butyl(dimethyl)silyl]oxy-8a-methyl-1-propan-2-yl-1,2,3,6,7,8-hexahydroazulen-5-one
• 化学式: C₂₀H₃₆O₂Si
• 分子量: 336.59
• InChiKey: LESCESMOGAAXOX-IMFGXOCKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.74
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1β,3α,3aα)-1,2,3,3a,4,5-hexahydro-3a-methyl-3-(1-methylethyl)-1-(tert-butyldimethylsilyloxy)-7(6H)-azulenone 在 N,N-二甲基丙烯基脲 、 pyr*(HF)x 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (1R,3S,6R,8aR)-3-hydroxy-6-(5-hydroxy-3-oxopentyl)-6,8a-dimethyl-1-propan-2-yl-2,3,7,8-tetrahydro-1H-azulen-5-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
• 作为产物：
  描述：

  2-methyl-3-methylene-8-penten-4-yl acetoacetate 在 吡啶 、 咪唑 、 Grubbs catalyst first generation 、 tris(dibenzylideneacetone)dipalladium (0) 、 Proton Sponge 、 三(2-呋喃基)膦 、 二氯乙基铝 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正庚烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 104.0h， 生成 (1β,3α,3aα)-1,2,3,3a,4,5-hexahydro-3a-methyl-3-(1-methylethyl)-1-(tert-butyldimethylsilyloxy)-7(6H)-azulenone
  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.