(3α,3aα)-2,3,3a,4,5,6-hexahydro-3a-methyl-3-(1-methylethyl)azulene-1,7-dione

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3α,3aα)-2,3,3a,4,5,6-hexahydro-3a-methyl-3-(1-methylethyl)azulene-1,7-dione
• 英文别名: 3-isopropyl-3a-methyl-2,3,3a,4,5,6-hexahydro-azulen-1,7-dione；(3R,3aR)-3a-methyl-3-propan-2-yl-3,4,5,6-tetrahydro-2H-azulene-1,7-dione
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: XPXMTEMWMZRRAJ-BXUZGUMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3α,3aα)-2,3,3a,4,5,6-hexahydro-3a-methyl-3-(1-methylethyl)azulene-1,7-dione 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 三氟甲磺酸三甲基硅酯 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.5h， 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-氧代-1-环庚烷甲酸甲酯 在 palladium dihydroxide 叔丁基过氧化氢 、 正丁基锂 、 三氟甲磺酸 、 sodium hydride 、 potassium carbonate 、 N,N-二异丙基乙胺 、 氯磷酸二甲酯 、 lithium chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 101.5h， 生成 (3α,3aα)-2,3,3a,4,5,6-hexahydro-3a-methyl-3-(1-methylethyl)azulene-1,7-dione
  参考文献：
  名称：

  An Expeditious Nazarov Cyclization Strategy toward the Hydroazulene Core of Guanacastepene A

  摘要：

  The hydroazulene core of guanacastepene A has been synthesized in five steps from commercially available starting materials using a classical Nazarov cyclization to install the stereochemistry in the cyclopentanone diastereoselectively. In the presence or absence of Lewis bases, a hydroazulenone or a spirocyclic ketone generated via a novel Wagner-Meerwein rearrangement is obtained with excellent selectivity and yield.

  DOI：

  10.1021/ol036433z

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.
• An Expeditious Nazarov Cyclization Strategy toward the Hydroazulene Core of Guanacastepene A
  作者：Pauline Chiu、Shuoliang Li

  DOI：10.1021/ol036433z

  日期：2004.2.1

  The hydroazulene core of guanacastepene A has been synthesized in five steps from commercially available starting materials using a classical Nazarov cyclization to install the stereochemistry in the cyclopentanone diastereoselectively. In the presence or absence of Lewis bases, a hydroazulenone or a spirocyclic ketone generated via a novel Wagner-Meerwein rearrangement is obtained with excellent selectivity and yield.