(+)-(1S,4R,Z)-1,3,3-trimethylbicyclo[2.2.1]heptane-2-one oxime

• 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: (+)-(1S,4R,Z)-1,3,3-trimethylbicyclo[2.2.1]heptane-2-one oxime
• 英文别名: (+)-fenchone oxime；(1S,4R)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-one oxime；(NZ)-N-[(1S,4R)-1,3,3-trimethyl-2-bicyclo[2.2.1]heptanylidene]hydroxylamine
• 化学式: C₁₀H₁₇NO
• 分子量: 167.251
• InChiKey: POYGWXWGOBEMAT-RZIOALPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(1S,4R,Z)-1,3,3-trimethylbicyclo[2.2.1]heptane-2-one oxime 、 1-碘代丙烷 在 sodium hydride 作用下， 以 二甲基亚砜 、 mineral oil 为溶剂， 以53%的产率得到(+)-(1S,4R)-1,3,3-trimethylbicyclo[2.2.1]heptane-2-one oxime O-propyl ether
  参考文献：
  名称：

  Stereochemistry of terpene derivatives. Part 8: synthesis of novel terpenoids from (1S,4R)- and (1R,4S)-fenchone and their comparative odour characteristics

  摘要：

  O-alkylation of (+) and (-)-fenchone oximes with various alkyl halides led to 20 novel ethers. Better results were obtained when mild reaction conditions were employed (i.e., aprotic, polar solvent and room temperature). The hydrolytic kinetic resolution of the O-glycidyl derivative was carried out using cobalt-salen catalysts. The best results were obtained when using (-)-(R,R)-catalyst: (-)-(R)-isomer was obtained with >90% de. The use of a (+)-(S,S)-catalyst gave the (-)-(S)-epoxide with only 67% de. However, the (S)-epoxide was obtained with >90% de when the (-)-(R)-diol was subjected to the Mitsunobu reaction. Significant fragrance diversity was observed between the homologous series of fenchone oxime ethers. More agreeable are scents of ethers derived from (-)-fenchone oxime. Their odours range from turpentine like and resinous to vegetable, floral or woody whereas the scents of (+)-ethers range from turpentine, resinous to onion like and slightly floral. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.06.012
• 作为产物：
  描述：

  (+)-葑酮 在 吡啶 、 盐酸羟胺 作用下， 以 乙醇 、 水 为溶剂， 反应 6.0h， 以83%的产率得到(+)-(1S,4R,Z)-1,3,3-trimethylbicyclo[2.2.1]heptane-2-one oxime
  参考文献：
  名称：

  Stereochemistry of terpene derivatives. Part 8: synthesis of novel terpenoids from (1S,4R)- and (1R,4S)-fenchone and their comparative odour characteristics

  摘要：

  O-alkylation of (+) and (-)-fenchone oximes with various alkyl halides led to 20 novel ethers. Better results were obtained when mild reaction conditions were employed (i.e., aprotic, polar solvent and room temperature). The hydrolytic kinetic resolution of the O-glycidyl derivative was carried out using cobalt-salen catalysts. The best results were obtained when using (-)-(R,R)-catalyst: (-)-(R)-isomer was obtained with >90% de. The use of a (+)-(S,S)-catalyst gave the (-)-(S)-epoxide with only 67% de. However, the (S)-epoxide was obtained with >90% de when the (-)-(R)-diol was subjected to the Mitsunobu reaction. Significant fragrance diversity was observed between the homologous series of fenchone oxime ethers. More agreeable are scents of ethers derived from (-)-fenchone oxime. Their odours range from turpentine like and resinous to vegetable, floral or woody whereas the scents of (+)-ethers range from turpentine, resinous to onion like and slightly floral. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.06.012

文献信息

• Stereochemistry of terpene derivatives. Part 8: synthesis of novel terpenoids from (1S,4R)- and (1R,4S)-fenchone and their comparative odour characteristics
  作者：Daniel Jan Strub、Lucyna Balcerzak、Maria Niewiadomska、Józef Kula、Magdalena Sikora、Julia Gibka、Stanisław Lochyński

  DOI：10.1016/j.tetasy.2014.06.012

  日期：2014.7

  O-alkylation of (+) and (-)-fenchone oximes with various alkyl halides led to 20 novel ethers. Better results were obtained when mild reaction conditions were employed (i.e., aprotic, polar solvent and room temperature). The hydrolytic kinetic resolution of the O-glycidyl derivative was carried out using cobalt-salen catalysts. The best results were obtained when using (-)-(R,R)-catalyst: (-)-(R)-isomer was obtained with >90% de. The use of a (+)-(S,S)-catalyst gave the (-)-(S)-epoxide with only 67% de. However, the (S)-epoxide was obtained with >90% de when the (-)-(R)-diol was subjected to the Mitsunobu reaction. Significant fragrance diversity was observed between the homologous series of fenchone oxime ethers. More agreeable are scents of ethers derived from (-)-fenchone oxime. Their odours range from turpentine like and resinous to vegetable, floral or woody whereas the scents of (+)-ethers range from turpentine, resinous to onion like and slightly floral. (C) 2014 Elsevier Ltd. All rights reserved.