<1S,2R,5R,6S,14R>-1,2,6-trimethyl-9-methylene-6-oxiranylbicyclo<3.3.1>nonane | 234078-09-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: <1S,2R,5R,6S,14R>-1,2,6-trimethyl-9-methylene-6-oxiranylbicyclo<3.3.1>nonane
• 英文别名: (2R)-2-[(1R,2S,5S,6R)-2,5,6-trimethyl-9-methylidene-2-bicyclo[3.3.1]nonanyl]oxirane
• CAS: 234078-09-2
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: GBZJCFNOFXKFLS-IKSZGEOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  <1S,2R,5R,6S,14R>-1,2,6-trimethyl-9-methylene-6-oxiranylbicyclo<3.3.1>nonane 在 高氯酸 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以63%的产率得到trifarienol A
  参考文献：
  名称：

  Total synthesis of optically active liverwort sesquiterpenes, trifarienols A and B, using phenylethylamine as a chiral auxiliary

  摘要：

  The imine of (rac)-2,3-dimethylcyclohexanone 10a with (S)-(-)-phenylethylamine was reacted with methyl acrylate to yield methyl (1'S,6'R)-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanoate 4a in 26% (97% eel)after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b, was used, the same product 4b was obtained in 59% yield (>99.5% ee) after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b and (R)-(+)-phenylethylamine were used, the reaction underwent in only 5% yield, the products being 4c, 12, 13, 14, and 15. Thus, the reaction of 3b with methyl acrylate is a matched case, while that of 3c is a mismatched case. These phenomena are explained by the nonbonded interaction of methyl acrylate with chiral phenylethylamine and the methyl group at the 6'-position of the cyclohexanone ring in the transition state. The propanoate product 4b was successfully transformed into liverwort sesquiterpene (+)-trifarienol A 1 and (-)-trifarienol B 2 in 10 steps. We have developed an HPLC method to determine the ees of 2,2-disubstituted and 2,2,3-trisubstituted cyclohexanones using the corresponding pentafluorophenyl esters. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00067-1
• 作为产物：
  描述：

  <1S,2R,5S>-6-formyl-1,2-dimethyl-9-methylenebicyclo<3.3.1>nonane 在 potassium tert-butylate 、 sodium hydride 、 二甲基亚砜 作用下， 以 四氢呋喃 为溶剂， 反应 1.17h， 生成 <1S,2R,5R,6S,14R>-1,2,6-trimethyl-9-methylene-6-oxiranylbicyclo<3.3.1>nonane
  参考文献：
  名称：

  Total synthesis of optically active liverwort sesquiterpenes, trifarienols A and B, using phenylethylamine as a chiral auxiliary

  摘要：

  The imine of (rac)-2,3-dimethylcyclohexanone 10a with (S)-(-)-phenylethylamine was reacted with methyl acrylate to yield methyl (1'S,6'R)-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanoate 4a in 26% (97% eel)after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b, was used, the same product 4b was obtained in 59% yield (>99.5% ee) after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b and (R)-(+)-phenylethylamine were used, the reaction underwent in only 5% yield, the products being 4c, 12, 13, 14, and 15. Thus, the reaction of 3b with methyl acrylate is a matched case, while that of 3c is a mismatched case. These phenomena are explained by the nonbonded interaction of methyl acrylate with chiral phenylethylamine and the methyl group at the 6'-position of the cyclohexanone ring in the transition state. The propanoate product 4b was successfully transformed into liverwort sesquiterpene (+)-trifarienol A 1 and (-)-trifarienol B 2 in 10 steps. We have developed an HPLC method to determine the ees of 2,2-disubstituted and 2,2,3-trisubstituted cyclohexanones using the corresponding pentafluorophenyl esters. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00067-1

文献信息

• Total synthesis of optically active liverwort sesquiterpenes, trifarienols A and B, using phenylethylamine as a chiral auxiliary
  作者：Motoo Tori、Kenji Hisazumi、Tomonari Wada、Masakazu Sono、Katsuyuki Nakashima

  DOI：10.1016/s0957-4166(99)00067-1

  日期：1999.3

  The imine of (rac)-2,3-dimethylcyclohexanone 10a with (S)-(-)-phenylethylamine was reacted with methyl acrylate to yield methyl (1'S,6'R)-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanoate 4a in 26% (97% eel)after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b, was used, the same product 4b was obtained in 59% yield (>99.5% ee) after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b and (R)-(+)-phenylethylamine were used, the reaction underwent in only 5% yield, the products being 4c, 12, 13, 14, and 15. Thus, the reaction of 3b with methyl acrylate is a matched case, while that of 3c is a mismatched case. These phenomena are explained by the nonbonded interaction of methyl acrylate with chiral phenylethylamine and the methyl group at the 6'-position of the cyclohexanone ring in the transition state. The propanoate product 4b was successfully transformed into liverwort sesquiterpene (+)-trifarienol A 1 and (-)-trifarienol B 2 in 10 steps. We have developed an HPLC method to determine the ees of 2,2-disubstituted and 2,2,3-trisubstituted cyclohexanones using the corresponding pentafluorophenyl esters. (C) 1999 Elsevier Science Ltd. All rights reserved.