(1β,4β,6α)-4-(Hydroxymethyl)-1,7,7-trimethylbicyclo<4.4.0>decan-3-one | 138801-67-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1β,4β,6α)-4-(Hydroxymethyl)-1,7,7-trimethylbicyclo<4.4.0>decan-3-one
• 英文别名: (1β,4β,6α)-4-(Hydroxymethyl)-1,7,7-trimethylbicyclo[4.4.0]decan-3-one；(3R,4aS,8aR)-3-(hydroxymethyl)-5,5,8a-trimethyl-3,4,4a,6,7,8-hexahydro-1H-naphthalen-2-one
• CAS: 138801-67-9
• 化学式: C₁₄H₂₄O₂
• 分子量: 224.343
• InChiKey: GFXXTRUGCMQOGJ-SCDSUCTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  Ethyl 4-(1,3,3-trimethyl-2-methylenecyclohexyl)-3-oxobutanoate 在 rhodium(II) acetate dimer 、 对甲苯磺酰叠氮 、 氨 、 lithium 、 三乙胺 作用下， 以 四氢呋喃 、 乙腈 、 苯 为溶剂， 反应 36.17h， 生成 (1β,4β,6α)-4-(Hydroxymethyl)-1,7,7-trimethylbicyclo<4.4.0>decan-3-one
  参考文献：
  名称：

  First total synthesis of a natural thapsane

  摘要：

  本文介绍了一种立体特异性的天然硫杂环庚烷 1 的首次全合成方法，其原料是现成的环庚二醇 8。

  DOI：

  10.1039/c39910001693

文献信息

• First total synthesis of a natural thapsane
  作者：Adusumilli Srikrishna、Kathiresan Krishnan

  DOI：10.1039/c39910001693

  日期：——

  A stereospecific first total synthesis of a natural thapsane 1, from the readily available cyclogeraniol 8, is described.

  本文介绍了一种立体特异性的天然硫杂环庚烷 1 的首次全合成方法，其原料是现成的环庚二醇 8。
• Stereospecific construction of multiple contiguous quaternary carbons. Total synthesis of (±)-cis,anti,cis-1,8,12,12-tetramethyl-4-oxatricyclo[6.4.0.02,6]dodecan-3-ol, a thapsane isolated from Thapsia villosa var minor
  作者：A. Srikrishna、K. Krishnan

  DOI：10.1021/jo00079a020

  日期：1993.12

  The details of the first total synthesis of a natural thapsane 1g containing three contiguous quaternary carbon atoms, starting from cyclogeraniol (9) is described. The Claisen rearrangement of 9 with methoxypropene in the presence of acatalytic amount of propionic acid produced ketone 10. Rhodium acetate-catalyzed intramolecular cyclopropanation of alpha-diazo-beta-keto ester 12, obtained from 10 via beta-keto ester 8, furnished cyclopropyl keto ester 7. Lithium in liquid ammonia reductive cleavage of cyclopropyl compound 7 gave a 1:1 mixture of hydrindanone 6 and ketol 13. Wittig methylenation of 6 furnished ester 21. Epoxidation of 21, followed by BF3-OEt2-catalyzed rearrangement of epoxide 23 afforded hemiacetal 25. Treatment of hemiacetal 25 with triethylsilane in trifluoroacetic acid furnished lactone 22, a degradation product of various thapsanes. Finally, DIBAH reduction of lactone 22 generated the thapsane 1g.