exo-bicyclo[2.2.1]heptan-2-yl 4-chlorobenzoate

• 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: exo-bicyclo[2.2.1]heptan-2-yl 4-chlorobenzoate
• 英文别名: [(1S,2S,4R)-2-bicyclo[2.2.1]heptanyl] 4-chlorobenzoate
• 化学式: C₁₄H₁₅ClO₂
• 分子量: 250.725
• InChiKey: SHVZAMZQJQNFKJ-CDMKHQONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  exo-bicyclo[2.2.1]heptan-2-yl 4-chlorobenzoate 在 甲基(三氟甲基)-1,3-二环氧丙烷 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以2%的产率得到4-Chloro-benzoic acid (1R,2R,4S)-6-oxo-bicyclo[2.2.1]hept-2-yl ester
  参考文献：
  名称：

  Oxyfunctionalization of Aliphatic Esters by Methyl(trifluoromethyl)dioxirane

  摘要：

  The oxidation of lineal, cyclic, and bicyclic aliphatic p-chlorobenzoic and p-chorobenzenesulfonic acid esters 2 with methyl(trifluoromethyl)dioxirane (TFDO) (1) occurs at positions in the hydrocarbon chain distant from the directing group with a significant degree of selectivity to give the corresponding keto or hydroxy esters. Compounds 2 are relatively deactivated with respect to this oxidation due to the electron-withdrawing nature of the ester moiety. Methylene C-alpha-H and C-beta-H bonds remain unchanged in all cases, but tertiary C-beta-H bonds undergo oxidation with TFDO (1). Stereoelectronic factors are used to explain the faster reaction rate in competition experiments for the oxidation of endo-norbornyl ester 2h than for its exo-isomer 2g.

  DOI：

  10.1021/jo9604189
• 作为产物：
  描述：

  降冰片烯 、 对氯苯甲酸 在 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 1,4-二氧六环 为溶剂， 反应 18.0h， 以90%的产率得到exo-bicyclo[2.2.1]heptan-2-yl 4-chlorobenzoate
  参考文献：
  名称：

  Copper(ii)-catalysed addition of O–H bonds to norbornene

  摘要：

  Cu(OTf)2是一种廉价且对空气和水分稳定的催化剂，可用于脂肪族和芳香族酸及醇对降冰片烯的O-H加成反应。

  DOI：

  10.1039/b509933a

文献信息

• Scalable, Electrochemical Oxidation of Unactivated C–H Bonds
  作者：Yu Kawamata、Ming Yan、Zhiqing Liu、Deng-Hui Bao、Jinshan Chen、Jeremy T. Starr、Phil S. Baran

  DOI：10.1021/jacs.7b03539

  日期：2017.6.7

  A practical electrochemical oxidation of unactivated C–H bonds is presented. This reaction utilizes a simple redox mediator, quinuclidine, with inexpensive carbon and nickel electrodes to selectively functionalize “deep-seated” methylene and methine moieties. The process exhibits a broad scope and good functional group compatibility. The scalability, as illustrated by a 50 g scale oxidation of sclareolide

  介绍了未活化的 C-H 键的实际电化学氧化。该反应利用简单的氧化还原介质奎宁环和廉价的碳和镍电极选择性地功能化“深层”亚甲基和次甲基部分。该工艺表现出广泛的范围和良好的官能团兼容性。可扩展性，如紫苏内酯 50 克规模氧化所示，预示着立即和广泛采用。
• Copper(ii)-catalysed addition of O–H bonds to norbornene
  作者：Jason G. Taylor、Neil Whittall、King Kuok (Mimi) Hii

  DOI：10.1039/b509933a

  日期：——

  Cu(OTf)2 is an inexpensive, air- and moisture-stable catalyst for the O–H addition of aliphatic and aromatic acids and alcohols to norbornene.

  Cu(OTf)2是一种廉价且对空气和水分稳定的催化剂，可用于脂肪族和芳香族酸及醇对降冰片烯的O-H加成反应。
• Cationic Iron-catalyzed Addition of Carboxylic Acids to Olefins
  作者：Kimihiro Komeyama、Yasuhiro Mieno、Syotaro Yukawa、Takayuki Morimoto、Ken Takaki

  DOI：10.1246/cl.2007.752

  日期：2007.6.5

  Cationic iron salts were found to be good catalysts for intra- and intermolecular addition of carboxylic acids to olefins, which afforded the corresponding esters in good yields.

  发现阳离子铁盐是羧酸与烯烃的分子内和分子间加成的良好催化剂，其以良好的产率提供相应的酯。
• Oxyfunctionalization of Aliphatic Esters by Methyl(trifluoromethyl)dioxirane
  作者：Gregorio Asensio、Gloria Castellano、Rossella Mello、M. E. González Núñez

  DOI：10.1021/jo9604189

  日期：1996.1.1

  The oxidation of lineal, cyclic, and bicyclic aliphatic p-chlorobenzoic and p-chorobenzenesulfonic acid esters 2 with methyl(trifluoromethyl)dioxirane (TFDO) (1) occurs at positions in the hydrocarbon chain distant from the directing group with a significant degree of selectivity to give the corresponding keto or hydroxy esters. Compounds 2 are relatively deactivated with respect to this oxidation due to the electron-withdrawing nature of the ester moiety. Methylene C-alpha-H and C-beta-H bonds remain unchanged in all cases, but tertiary C-beta-H bonds undergo oxidation with TFDO (1). Stereoelectronic factors are used to explain the faster reaction rate in competition experiments for the oxidation of endo-norbornyl ester 2h than for its exo-isomer 2g.