2-(2-(4-bromobenzoyl)cyclohex-2-en-1-yl)-1-(4-bromophenyl)ethanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(2-(4-bromobenzoyl)cyclohex-2-en-1-yl)-1-(4-bromophenyl)ethanone
• 英文别名: 2-[(1R)-2-(4-bromobenzoyl)cyclohex-2-en-1-yl]-1-(4-bromophenyl)ethanone
• 化学式: C₂₁H₁₈Br₂O₂
• 分子量: 462.181
• InChiKey: XPTQEXIXZHRLLE-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  戊二醛 在 N-乙酰基-L-半胱氨酸甲酯 、 potassium tert-butylate 、 水 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 48.0h， 生成 2-(2-(4-bromobenzoyl)cyclohex-2-en-1-yl)-1-(4-bromophenyl)ethanone
  参考文献：
  名称：

  Enantioselective Rauhut−Currier Reactions Promoted by Protected Cysteine

  摘要：

  We report highly enantioselective examples of the Rauhut-Currier cycloisomerization reaction (the "vinylogous Morita-Baylis-Hillman reaction"). The reaction is highly practical and is catalyzed by a commercially available derivative of the proteinogenic amino acid cysteine. Reactions are conducted in the presence of potassium tert-butoxide and a critical concentration of water in bulk acetonitrile. A mechanistic model is advanced that may account for reaction selectivity that is predicated on organizational chelation of K ion in the product-determining step in which the Cys derivative undergoes limination.

  DOI：

  10.1021/ja067139f

文献信息

• Enantioselective intramolecular Rauhut–Currier reaction catalyzed by chiral phosphinothiourea
  作者：Jing-Jing Gong、Tian-Ze Li、Kun Pan、Xin-Yan Wu

  DOI：10.1039/c0cc04412a

  日期：——

  Chiral organophosphine-catalyzed enantioselective Rauhut-Currier reaction has been disclosed for the first time. With L-valine-derived phosphinothiourea, the intramolecular Rauhut-Currier reaction of bis(enones) was achieved in good yields (up to 99%) with excellent enantioselectivities (up to 99.4% ee).

  首次公开了手性有机膦催化的对映选择性Rauhut-Currier反应。用L-缬氨酸衍生的膦硫脲，以良好的对映选择性（高达99.4％ee）以良好的产率（高达99％）实现了双（烯酮）的分子内Rauhut-Currier反应。
• A Highly Nucleophilic Multifunctional Chiral Phosphane-Catalyzed Asymmetric Intramolecular Rauhut-Currier Reaction
  作者：Xiao-Nan Zhang、Min Shi

  DOI：10.1002/ejoc.201200940

  日期：2012.11

  An asymmetric variant of the intramolecular Rauhut–Currier (RC) reaction can be achieved using a highly nucleophilic multifunctional chiral phosphane; the corresponding cyclopentene and cyclohexene derivatives are produced in moderate to good yields and with good to excellent enantioselectivities.

  使用高度亲核的多功能手性磷烷可以实现分子内 Rauhut-Currier (RC) 反应的不对称变体；相应的环戊烯和环己烯衍生物以中等至良好的收率和良好至极好的对映选择性生产。
• Asymmetric Intramolecular Rauhut–Currier Reaction and Its Desymmetric Version via Double Thiol/Phase-Transfer Catalysis
  作者：Ying Jiang、Yang Yang、Qing He、Wei Du、Ying-Chun Chen

  DOI：10.1021/acs.joc.0c01293

  日期：2020.8.21

  intramolecular Rauhut–Currier reaction of linear bis(enones) has been achieved via double activation catalysis of thiols and phase transfer substances, furnishing both enantioenriched cyclohexene and cyclopentene derivatives (up to 95% ee). Furthermore, the desymmetric version of prochiral substrates was developed under similar catalysis, producing the frameworks bearing an additional tertiary or even quaternary

  线性双（烯酮）的不对称分子内Rauhut-Currier反应是通过硫醇和相转移物质的双重活化催化实现的，提供了对映体富集的环己烯和环戊烯衍生物（ee高达95％）。此外，前手性底物的不对称形式是在相似的催化作用下开发的，产生的骨架带有一个附加的叔或什至四元立体异构中心，具有中等到极好的非对映和对映选择性（高达95％ee，> 19：1 dr）。
• Development of a Cysteine-Catalyzed Enantioselective Rauhut−Currier Reaction
  作者：Carrie E. Aroyan、Alpay Dermenci、Scott J. Miller

  DOI：10.1021/jo101018t

  日期：2010.9.3

  Herein, we report a full account of the development of an enantioselective Rauhut-Currier process that affords products in high yields and enantioselectivities using a cysteine-based catalyst. While traditional Morita-Baylis-Hillman catalysts were found to be essentially ineffective, various derivatives of protected cysteine were found to exhibit extraordinary reactivity and enantiotopic control. Extensive screening of reaction conditions led us to discover the enhanced effects of water as an additive and the chelating power of potassium in achieving higher enantiomer ratios. Mechanistic experiments also provided insight on the potential mechanism of the reaction in addition to possible transition states that provide the absolute stereochemistry formed in the observed products. Also included is a brief survey of the reaction scope involving different ring sizes as well as functionalized substrates.