(S)-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: (S)-2-(2-(4-bromobenzoyl)cyclohex-2-en-1-yl)-1-(4-bromophenyl)ethanone
• 英文别名: 2-[(1S)-2-(4-bromobenzoyl)cyclohex-2-en-1-yl]-1-(4-bromophenyl)ethanone
• 化学式: C₂₁H₁₈Br₂O₂
• 分子量: 462.181
• InChiKey: XPTQEXIXZHRLLE-INIZCTEOSA-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

• 作为反应物：
  描述：

  (S)-2-(2-(4-bromobenzoyl)cyclohex-2-en-1-yl)-1-(4-bromophenyl)ethanone 、 2,4-二硝基苯肼 在 硫酸 作用下， 以 乙醇 、 水 为溶剂， 反应 24.0h， 以45%的产率得到
  参考文献：
  名称：

  Development of a Cysteine-Catalyzed Enantioselective Rauhut−Currier Reaction

  摘要：

  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.

  DOI：

  10.1021/jo101018t
• 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 (S)-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

• Ferrocene-based bifunctional organocatalyst for highly enantioselective intramolecular Rauhut–Currier reaction
  作者：Xiaowei Zhou、Huifang Nie、Xian Liu、Xiaomei Long、Ru Jiang、Weiping Chen

  DOI：10.1016/j.catcom.2018.12.016

  日期：2019.3

  showed good performance in enantioselective intramolecular Rauhut–Currier reaction of bis(enones), giving the corresponding products in good yield with up to 98% ee. Moreover, with amino acid derived amide-phosphine B3, optically active α-methylene-δ-valerolactone was obtained in 88% yield and > 99.9% ee utilizing the enantioselective intramolecular Rauhut-Currier reaction of chalcone derivative.

  已经设计和合成了三系列新颖的基于二茂铁的双官能手性膦。硫脲磷化氢A7在双（烯酮）对映选择性分子内的Rauhut-Currier反应中显示出良好的性能，以高达98％ee的产率提供了相应的产物。此外，利用氨基酸衍生的酰胺-膦B3，利用查尔酮衍生物的对映选择性分子内Rauhut-Currier反应，以88％的收率和＞ 99.9％ee的ee获得了光学活性的α-亚甲基-δ-戊内酯。
• 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.
• Enantioselective Rauhut−Currier Reactions Promoted by Protected Cysteine
  作者：Carrie E. Aroyan、Scott J. Miller

  DOI：10.1021/ja067139f

  日期：2007.1.1

  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.