<1'S,6'R>-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanal | 234078-00-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <1'S,6'R>-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanal
• 英文别名: 3-[(1S,2R)-1,2-dimethyl-6-oxocyclohexyl]propanal
• CAS: 234078-00-3
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: OPIDPLZKQOFZAL-KOLCDFICSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  <1'S,6'R>-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanal 在 盐酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 以86 %的产率得到rac-6-hydroxy-1,2-dimethylbicyclo[3.3.1]nonan-9-one
  参考文献：
  名称：

  (+)-Lemnardosinane A 的不对称全合成

  摘要：

  以( S )-香芹酮为原料，完成了(+)-柠檬香烷A（一种罕见的重排倍半萜类化合物）的不对称全合成。该合成的主要特征是利用分子内羟醛反应形成双环[3.3.1]壬烷骨架、立体选择性引入炔基以及通过分子内频哪醇偶联立体选择性形成三环骨架。

  DOI：

  10.1021/acs.orglett.4c01384
• 作为产物：
  描述：

  2,3-dimethylcyclohexanone 在 lithium aluminium tetrahydride 、 草酰氯 、 对甲苯磺酸 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醚 、 苯 为溶剂， 反应 198.25h， 生成 <1'S,6'R>-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanal
  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.