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

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3α,3aα)-7,7-ethylenedioxy-3,3a,4,5,6,7-hexahydro-3a-methyl-3-(1-methylethyl)-1(2H)-azulenone
• 英文别名: (3'R,3'aR)-3'a-methyl-3'-propan-2-ylspiro[1,3-dioxolane-2,7'-3,4,5,6-tetrahydro-2H-azulene]-1'-one
• 化学式: C₁₆H₂₄O₃
• 分子量: 264.365
• InChiKey: RLSIZBKGXBLZHF-IUODEOHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.81
• 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：

  (3α,3aα)-7,7-ethylenedioxy-3,3a,4,5,6,7-hexahydro-3a-methyl-3-(1-methylethyl)-1(2H)-azulenone 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 (2β,3α,3aα)-2-bromo-7,7-ethylenedioxy-3,3a,4,5,6,7-hexahydro-3a-methyl-3-(1-methylethyl)-1(2H)-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
• 作为产物：
  描述：

  2-methyl-3-methylene-8-penten-4-yl acetoacetate 在 Grubbs catalyst first generation 、 tris(dibenzylideneacetone)dipalladium (0) 、 Proton Sponge 、 三(2-呋喃基)膦 、 三氟甲磺酸三甲基硅酯 、 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 、 甲苯 为溶剂， 反应 107.33h， 生成 (3α,3aα)-7,7-ethylenedioxy-3,3a,4,5,6,7-hexahydro-3a-methyl-3-(1-methylethyl)-1(2H)-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.