rel-(4R,5S,6S)-6-Acetyl-4,8,8-trimethylspiro<4.4>nonan-1-one

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: rel-(4R,5S,6S)-6-Acetyl-4,8,8-trimethylspiro<4.4>nonan-1-one
• 英文别名: (1S,5R,9R)-9-acetyl-1,7,7-trimethylspiro[4.4]nonan-4-one
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: CUHXQQDXTGHGMQ-NURSFMCSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,1-ethylenedioxy-3,5,5-trimethylcyclohex-3-ene 在 palladium on activated charcoal 二甲基硫 、 三氟化硼乙醚 、 氢气 、 对甲苯磺酸 、 臭氧 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 苯 为溶剂， -78.0~25.0 ℃ 、303.98 kPa 条件下， 反应 5.0h， 生成 rel-(4R,5S,6S)-6-Acetyl-4,8,8-trimethylspiro<4.4>nonan-1-one
  参考文献：
  名称：

  Spiroannulation approach to pentalenene, an angular triquinane sesquiterpene

  摘要：

  The route to the angular triquinane (+/-)-pentalenene (la) followed from an efficient geminal acylation of the acetal of isophorone or its homolog 6b by 1,2-bis((trimethylsilyl) oxy) cyclobutene (3) in the presence of boron trifluoride etherate. Ring cleavage and reclosure (9 --> 11) secured the required spiro[4.4]nonane system with a pendant ketone function in place for the closure of the final, central : I ring. The relative stereochemistry at C-9 was established during hydrogenation over palladium of the C-3 double bond of 11, but the facial selectivity was determined by the mode of reduction of the conjugated, orthogonal double bond at C-6 of 11. After cyclization to the enone 17b, the synthesis was completed by reductions of both the double bond and the ketone and simple dehydration. The 9-epi isomer (26) of (+/-)-pentalenene was synthesized also.

  DOI：

  10.1021/jo00080a018

文献信息

• Spiroannulation approach to pentalenene, an angular triquinane sesquiterpene
  作者：Y.-J. Wu、Y.-Y. Zhu、D. Jean Burnell

  DOI：10.1021/jo00080a018

  日期：1994.1

  The route to the angular triquinane (+/-)-pentalenene (la) followed from an efficient geminal acylation of the acetal of isophorone or its homolog 6b by 1,2-bis((trimethylsilyl) oxy) cyclobutene (3) in the presence of boron trifluoride etherate. Ring cleavage and reclosure (9 --> 11) secured the required spiro[4.4]nonane system with a pendant ketone function in place for the closure of the final, central : I ring. The relative stereochemistry at C-9 was established during hydrogenation over palladium of the C-3 double bond of 11, but the facial selectivity was determined by the mode of reduction of the conjugated, orthogonal double bond at C-6 of 11. After cyclization to the enone 17b, the synthesis was completed by reductions of both the double bond and the ketone and simple dehydration. The 9-epi isomer (26) of (+/-)-pentalenene was synthesized also.