2-(3-oxocyclohexyl)malonic acid di-tert-butyl ester | 847151-91-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-(3-oxocyclohexyl)malonic acid di-tert-butyl ester
• 英文别名: Ditert-butyl 2-(3-oxocyclohexyl)propanedioate
• CAS: 847151-91-1
• 化学式: C₁₇H₂₈O₅
• 分子量: 312.406
• InChiKey: PHLKBCVJYJEICD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-(3-oxocyclohexyl)malonic acid di-tert-butyl ester 在 氟乙酸 、 水 作用下， 生成 2-(3-氧代环己基)-丙二酸二甲酯
  参考文献：
  名称：

  Asymmetric Michael Addition of Malonate Anions to Prochiral Acceptors Catalyzed by l-Proline Rubidium Salt

  摘要：

  L-Proline rubidium salt catalyzes the asymmetric Michael addition of malonate anions to prochiral enones and enals. This method can be applied to a wide range of substrates to give adducts with a predictable absolute configuration: (S)-adducts from (E)-enones/enals and (R)-adducts from cyclic (Z)-enones. Both the secondary amine moiety and the carboxylate moiety are critical for the catalytic activity and asymmetric induction. Varying the countercation also affects the reaction course. High enantiomeric excesses were attained when di(tert-butyl) malonate was added to (E)-enones in the presence of CsF. The stereochemistry of the Michael reaction indicates that asymmetric induction takes place via enantioface discrimination involving the acceptor alpha-carbon atom rather than the beta-carbon atom.

  DOI：

  10.1021/jo960216c
• 作为产物：
  描述：

  2-环己烯-1-酮 、 丙二酸二叔丁酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以94%的产率得到2-(3-oxocyclohexyl)malonic acid di-tert-butyl ester
  参考文献：
  名称：

  催化电子活化作为向烯丙醇中添加稳定亲核试剂的工具

  摘要：

  本文介绍了通过使用铝催化的转移氢化作用来活化2-cyclohexen-1-ol（1）和2-cyclopenten-1-ol（11）。已证明电子活化的底物易于偶联物加成，并且当随后通过一锅法恢复醇官能团时，这导致亲核试剂间接加成到烯丙基醇中。这种新颖的方法被称为催化电子活化。

  DOI：

  10.1016/j.tet.2004.10.009
• 作为试剂：
  描述：

  丙二酸二叔丁酯 、 2-环己烯醇 在 二甲基氯化铝 、 sodium hydride 、 2-(3-oxocyclohexyl)malonic acid di-tert-butyl ester 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 91.0h， 生成 2-(3-hydroxycyclohexyl)malonic acid di-tert-butyl ester
  参考文献：
  名称：

  催化电子活化作为向烯丙醇中添加稳定亲核试剂的工具

  摘要：

  本文介绍了通过使用铝催化的转移氢化作用来活化2-cyclohexen-1-ol（1）和2-cyclopenten-1-ol（11）。已证明电子活化的底物易于偶联物加成，并且当随后通过一锅法恢复醇官能团时，这导致亲核试剂间接加成到烯丙基醇中。这种新颖的方法被称为催化电子活化。

  DOI：

  10.1016/j.tet.2004.10.009

文献信息

• Asymmetric Michael addition reactions using a chiral La–Na aminodiolate catalyst
  作者：N Prabagaran、G Sundararajan

  DOI：10.1016/s0957-4166(02)00240-9

  日期：2002.6

  (R,R)-(+)-2-[Benzyl-(2-hydroxy-2-phenylethyl)amino]-1-phenylethanol 1 is used as a chiral ligand in the synthesis of an optically active lanthanum-sodium amino diol complex LS-1. This heterobimetallic catalyst is quite effective its an asymmetric catalyst for various Michael addition reactions, H-1 NMR Study indicates the co-ordination of enone to the central lanthanum atom in LS-1. The reaction conditions were optimized and the adducts were obtained in high yield with moderate to high enantiomeric excess under extremely mild conditions. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Asymmetric Michael Addition of Malonate Anions to Prochiral Acceptors Catalyzed by <scp>l</scp>-Proline Rubidium Salt
  作者：Masahiko Yamaguchi、Tai Shiraishi、Masahiro Hirama

  DOI：10.1021/jo960216c

  日期：1996.1.1

  L-Proline rubidium salt catalyzes the asymmetric Michael addition of malonate anions to prochiral enones and enals. This method can be applied to a wide range of substrates to give adducts with a predictable absolute configuration: (S)-adducts from (E)-enones/enals and (R)-adducts from cyclic (Z)-enones. Both the secondary amine moiety and the carboxylate moiety are critical for the catalytic activity and asymmetric induction. Varying the countercation also affects the reaction course. High enantiomeric excesses were attained when di(tert-butyl) malonate was added to (E)-enones in the presence of CsF. The stereochemistry of the Michael reaction indicates that asymmetric induction takes place via enantioface discrimination involving the acceptor alpha-carbon atom rather than the beta-carbon atom.
• Catalytic electronic activation as a tool for the addition of stabilised nucleophiles to allylic alcohols
  作者：Phillip J. Black、Michael G. Edwards、Jonathan M.J. Williams

  DOI：10.1016/j.tet.2004.10.009

  日期：2005.1

  describes the activation of 2-cyclohexen-1-ol (1) and 2-cyclopenten-1-ol (11) through the use of aluminium-catalysed transfer hydrogenation. The electronically activated substrates are demonstrated to undergo facile conjugate addition and, when the alcohol functional group is subsequently restored in a one-pot procedure, this leads to an indirect addition of nucleophiles to allylic alcohols. This novel

  本文介绍了通过使用铝催化的转移氢化作用来活化2-cyclohexen-1-ol（1）和2-cyclopenten-1-ol（11）。已证明电子活化的底物易于偶联物加成，并且当随后通过一锅法恢复醇官能团时，这导致亲核试剂间接加成到烯丙基醇中。这种新颖的方法被称为催化电子活化。