(4α,5β)-5-methyl-4-(1-methylethyl)-5-(4-pentenyl)-1-cyclopenten-1-yl trifluoromethanesulfonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (4α,5β)-5-methyl-4-(1-methylethyl)-5-(4-pentenyl)-1-cyclopenten-1-yl trifluoromethanesulfonate
• 英文别名: [(4R,5R)-5-methyl-5-pent-4-enyl-4-propan-2-ylcyclopenten-1-yl] trifluoromethanesulfonate
• 化学式: C₁₅H₂₃F₃O₃S
• 分子量: 340.407
• InChiKey: QNWIJMMDSIGYIG-TZMCWYRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4α,5β)-5-methyl-4-(1-methylethyl)-5-(4-pentenyl)-1-cyclopenten-1-yl trifluoromethanesulfonate 在 吡啶 、 4-二甲氨基吡啶 、 Grubbs catalyst first generation 、 tris(dibenzylideneacetone)dipalladium (0) 、 碳酸氢钠 、 sodium carbonate 、 potassium carbonate 、 间氯过氧苯甲酸 、 1,4-双(二苯基膦)丁烷 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 20.5h， 生成 (1α,3β,8aα)-1,2,3,5,6,7,8,8a-octahydro-8a-methyl-1-(1-methylethyl) 3-(trimethylacetoxy)azulene-5-ol
  参考文献：
  名称：

  胍卡斯汀的水az环体系的合成。

  摘要：

  [反应：请参阅文字]使用EtAlCl（2）引发的γ-δ-不饱和酮13环化反应，以构建2,2,26，完成了十二步合成26，即功能化的瓜纳卡斯汀（1）的氢氮烯酮环。 3-三取代的环戊酮14，乙烯基溴化镁与三氟甲磺酸烯醇酯17的钯催化偶合以制备三烯21，以及三烯21的烯烃复分解反应形成关键的水腈20。

  DOI：

  10.1021/ol0069756
• 作为产物：
  描述：

  2-methyl-3-methylene-8-penten-4-yl acetoacetate 在 Proton Sponge 、 二氯乙基铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正庚烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 29.5h， 生成 (4α,5β)-5-methyl-4-(1-methylethyl)-5-(4-pentenyl)-1-cyclopenten-1-yl trifluoromethanesulfonate
  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.
• Synthesis of the Hydroazulene Ring System of Guanacastepene
  作者：Barry B. Snider、Natalie A. Hawryluk

  DOI：10.1021/ol0069756

  日期：2001.2.1

  [reaction: see text] A 12-step synthesis of 26, the functionalized hydroazulenone ring of guanacastepene (1), has been completed using the EtAlCl(2)-initiated cyclization of gamma,delta-unsaturated ketone 13 to construct 2,2,3-trisubstituted cyclopentanone 14, the palladium-catalyzed coupling of vinylmagnesium bromide with enol triflate 17 to prepare triene 21, and olefin metathesis of triene 21 to

  [反应：请参阅文字]使用EtAlCl（2）引发的γ-δ-不饱和酮13环化反应，以构建2,2,26，完成了十二步合成26，即功能化的瓜纳卡斯汀（1）的氢氮烯酮环。 3-三取代的环戊酮14，乙烯基溴化镁与三氟甲磺酸烯醇酯17的钯催化偶合以制备三烯21，以及三烯21的烯烃复分解反应形成关键的水腈20。