Adamantane-2-carboxylic acid (1S,2S,3S,5R)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl ester | 1026087-02-4

• 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: Adamantane-2-carboxylic acid (1S,2S,3S,5R)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl ester
• 英文别名: [(1S,2S,3S,5R)-2,6,6-trimethyl-3-bicyclo[3.1.1]heptanyl] adamantane-2-carboxylate
• CAS: 1026087-02-4
• 化学式: C₂₁H₃₂O₂
• 分子量: 316.484
• InChiKey: UCXNCFDKJXWGMG-QNKWNLTOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苯甲酰氯 、 Adamantane-2-carboxylic acid (1S,2S,3S,5R)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl ester 在 potassium diisopropylamide 、 lithium tert-butoxide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 生成 [(1S,2S,3S,5R)-2,6,6-trimethyl-3-bicyclo[3.1.1]heptanyl] 2-benzoyladamantane-2-carboxylate
  参考文献：
  名称：

  Enhanced Enantio- and Diastereoselectivity via Confinement and Cation Binding:  Yang Photocyclization of 2-Benzoyladamantane Derivatives within Zeolites

  摘要：

  Irradiation of 2-benzoyladamantane derivatives in zeolites yields the endo-cyclobutanols as the only photoproduct via a gamma-hydrogen abstraction process. The cyclobutanols readily undergo retro-aldol reaction to give delta-ketoesters. The enantiomeric excess (ee) in the endo-cyclobutanols is measured by monitoring the ee in the ketoesters. Whereas in solution the ee in the product ketoester is zero, within achiral NaY zeolite, in the presence of a chiral inductor such as pseudoephedrine, ee's up to 28% have been obtained. The influence of zeolite on several chiral esters of 2-benzoyladamantane-2-carboxylic acids has also been examined. Whereas in solution the diastereomeric excess is <15%, in zeolite the delta-ketoesters are obtained in 79% de (best examples). Ab initio computations suggest that enhancement of chiral induction within zeolites is likely to be due to cation complexation with the reactant ketone. Alkali ion-organic interaction, a powerful tool, is waiting to be fully exploited in photochemical and thermal reactions. In this context zeolites could be a useful medium as one could view them as a reservoir of "naked" alkali ions that are only partially coordinated to the zeolite walls.

  DOI：

  10.1021/jo0260793
• 作为产物：
  描述：

  2-methoxymethylene adamantane 在 chromium(VI) oxide 、 草酰氯 、 硫酸 、 水 、 N,N-二甲基甲酰胺 作用下， 以 乙醚 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 6.0h， 生成 Adamantane-2-carboxylic acid (1S,2S,3S,5R)-2,6,6-trimethyl-bicyclo[3.1.1]hept-3-yl ester
  参考文献：
  名称：

  Enhanced Enantio- and Diastereoselectivity via Confinement and Cation Binding:  Yang Photocyclization of 2-Benzoyladamantane Derivatives within Zeolites

  摘要：

  Irradiation of 2-benzoyladamantane derivatives in zeolites yields the endo-cyclobutanols as the only photoproduct via a gamma-hydrogen abstraction process. The cyclobutanols readily undergo retro-aldol reaction to give delta-ketoesters. The enantiomeric excess (ee) in the endo-cyclobutanols is measured by monitoring the ee in the ketoesters. Whereas in solution the ee in the product ketoester is zero, within achiral NaY zeolite, in the presence of a chiral inductor such as pseudoephedrine, ee's up to 28% have been obtained. The influence of zeolite on several chiral esters of 2-benzoyladamantane-2-carboxylic acids has also been examined. Whereas in solution the diastereomeric excess is <15%, in zeolite the delta-ketoesters are obtained in 79% de (best examples). Ab initio computations suggest that enhancement of chiral induction within zeolites is likely to be due to cation complexation with the reactant ketone. Alkali ion-organic interaction, a powerful tool, is waiting to be fully exploited in photochemical and thermal reactions. In this context zeolites could be a useful medium as one could view them as a reservoir of "naked" alkali ions that are only partially coordinated to the zeolite walls.

  DOI：

  10.1021/jo0260793