[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 2-benzoyladamantane-2-carboxylate | 314041-51-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 2-benzoyladamantane-2-carboxylate
• CAS: 314041-51-5
• 化学式: C₂₈H₃₈O₃
• 分子量: 422.608
• InChiKey: UFCYXQSRTDENEP-WNCFDTQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 2-benzoyladamantane-2-carboxylate 在 NaY zeolite 作用下， 以 正己烷 为溶剂， 反应 1.25h， 生成 (1R,2R,3S,4R,5S)-4-Benzoyl-adamantane-2-carboxylic acid (1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl ester 、 (1S,2S,3R,4S,5R)-4-Benzoyl-adamantane-2-carboxylic acid (1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl 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
• 作为产物：
  描述：

  2-methoxymethylene adamantane 在 chromium(VI) oxide 、 草酰氯 、 硫酸 、 水 、 potassium diisopropylamide 、 N,N-二甲基甲酰胺 、 lithium tert-butoxide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 7.5h， 生成 [(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 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

文献信息

• Enhanced Enantio- and Diastereoselectivity via Confinement and Cation Binding:  Yang Photocyclization of 2-Benzoyladamantane Derivatives within Zeolites
  作者：Arunkumar Natarajan、Abraham Joy、Lakshmi S. Kaanumalle、John R. Scheffer、V. Ramamurthy

  DOI：10.1021/jo0260793

  日期：2002.11.1

  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.