(E)-3-(3-bromophenyl)-1-(1-methyl-1H-imidazol-2-yl)prop-2-en-1-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-3-(3-bromophenyl)-1-(1-methyl-1H-imidazol-2-yl)prop-2-en-1-one
• 英文别名: (E)-3-(3-bromophenyl)-1-(1-methylimidazol-2-yl)prop-2-en-1-one
• 化学式: C₁₃H₁₁BrN₂O
• 分子量: 291.147
• InChiKey: VBDUDYANLALWOS-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  34.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-氰基-3-四氢噻吩酮 、 (E)-3-(3-bromophenyl)-1-(1-methyl-1H-imidazol-2-yl)prop-2-en-1-one 在 4,4'-二甲基-2,2'-联吡啶 、 copper(II) bis(trifluoromethanesulfonate) 、 四丁基氢氧化铵 作用下， 以 二氯甲烷 、 甲醇 为溶剂， 反应 0.03h， 生成 3-(3-bromophenyl)-5-(1-methyl-1H-imidazol-2-yl)-2-methylene-5-oxopentanenitrile
  参考文献：
  名称：

  Direct Access to Highly Enantioenriched α-Branched Acrylonitriles through a One-Pot Sequential Asymmetric Michael Addition/Retro-Dieckmann/Retro-Michael Fragmentation Cascade

  摘要：

  A highly enantioselective synthesis of alpha-branched acrylonitriles is reported featuring a one-pot sequential asymmetric Michael addition/retro-Dieckmann/retro-Michael fragmentation cascade. The method, which relies on a solid, bench-stable, and commercially available acrylonitrile surrogate, is practical, scalable, and highly versatile and provides a direct access to a wide range of enantioenriched nitrite-containing building blocks. Most importantly, the method offers a new tool to incorporate an acrylonitrile moiety in an asymmetric fashion.

  DOI：

  10.1021/acs.orglett.0c02079
• 作为产物：
  描述：

  间溴苯甲醛 、 1-(1-甲基-1H-咪唑-2-基)乙酮 在 potassium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 12.0h， 以65%的产率得到(E)-3-(3-bromophenyl)-1-(1-methyl-1H-imidazol-2-yl)prop-2-en-1-one
  参考文献：
  名称：

  α，β-不饱和2-酰基咪唑类对瞬态羧酸氧鎓盐的非对映选择性捕获

  摘要：

  通过开发环丙烯羧酸与α，β-不饱和2-酰基咪唑的非对映选择性反应，我们在此报道了瞬态羧酸氧鎓叶立德的Michael型捕集。这种转化为在温和的反应条件下以高非对映选择性（高达> 95：5 dr）以高收率（60–99％）构建有价值的γ-丁烯内酯衍生物提供了一种直接方法。

  DOI：

  10.1002/adsc.202000701

文献信息

• Diastereoselective Trapping of Transient Carboxylic Oxonium Ylides with α,β‐Unsaturated 2‐Acyl Imidazoles
  作者：Mengchu Zhang、Tianyuan Zhang、Dan Zhang、Wenhao Hu

  DOI：10.1002/adsc.202000701

  日期：2020.11.4

  By developing a diastereoselective reaction of cyclopropene carboxylic acids with α,β‐unsaturated 2‐acyl imidazoles, we reported here a Michael‐type trapping of transient carboxylic oxonium ylides. This transformation provides a direct approach for the construction of valuable γ‐butenolide derivatives in good yields (60–99%) with high diastereoselectivities (up to >95:5 dr) under mild reaction conditions

  通过开发环丙烯羧酸与α，β-不饱和2-酰基咪唑的非对映选择性反应，我们在此报道了瞬态羧酸氧鎓叶立德的Michael型捕集。这种转化为在温和的反应条件下以高非对映选择性（高达> 95：5 dr）以高收率（60–99％）构建有价值的γ-丁烯内酯衍生物提供了一种直接方法。
• Asymmetric Umpolung (3+2) Cycloadditions of Iminoesters with α,β-Unsaturated-2-acyl Imidazoles for the Synthesis of Substituted Pyrrolidines
  作者：Mamta Gill、Arko Das、Vinod K. Singh

  DOI：10.1021/acs.orglett.2c01438

  日期：2022.8.12

  enantioselective (3+2) cycloaddition reaction of iminoesters occurring with opposite regioselectivity is reported. This reaction provides chiral polysubstituted pyrrolidines with high enantioselectivities (up to 97%), diastereoselectivities (>20:1), and yields (up to 99%). Interestingly, changing the alpha-substituents of the iminoesters from an aryl to an aliphatic (benzyl) group or hydrogen resulted

  报道了以相反的区域选择性发生的亚氨基酯的对映选择性 (3+2) 环加成反应。该反应提供了具有高对映选择性（高达 97%）、非对映选择性（>20:1）和产率（高达 99%）的手性多取代吡咯烷。有趣的是，将亚氨基酯的 α-取代基从芳基变为脂肪族（苄基）基团或氢会导致形成正常的 (3+2) 环加成产物，同时具有出色的对映选择性。
• Enantioselective synthesis of substituted 1-pyrrolines via Michael addition of iminoesters with α,β-unsaturated 2-acyl imidazoles catalyzed by chiral Cu(I)-BPE complex
  作者：Mamta Gill、Vinod K. Singh

  DOI：10.1016/j.tetlet.2023.154555

  日期：2023.6

  A highly chemo-, diastereo-, and enantioselective Cu(I)-1,2-Bis((2S,5S)-2,5-diphenylphospholano)ethane (BPE) catalyzed Michael addition of iminoesters to α, β-unsaturated 2-acyl imidazoles at 0 °C and subsequent silica-assisted cyclization of Michael adducts into highly functionalized 1-pyrrolines bearing two contiguous stereocenters (up to >20: 1 cr, > 20: 1 dr, and 99% ee) has been described.

  一种高度化学、非对映和对映选择性的 Cu(I)-1,2-双((2 S ,5 S )-2,5-二苯基膦基)乙烷 (BPE) 催化亚氨基酯迈克尔加成到α , β -不饱和0 °C 下的2-酰基咪唑和随后的二氧化硅辅助迈克尔加合物环化成带有两个连续立体中心的高度功能化的 1-吡咯啉（高达 >20: 1 cr，> 20: 1 dr，和 99% ee）已被描述.
• Direct Access to Highly Enantioenriched α-Branched Acrylonitriles through a One-Pot Sequential Asymmetric Michael Addition/Retro-Dieckmann/Retro-Michael Fragmentation Cascade
  作者：Nicolas Duchemin、Martin Cattoen、Oscar Gayraud、Silvia Anselmi、Bilal Siddiq、Roberto Buccafusca、Marc Daumas、Vincent Ferey、Michael Smietana、Stellios Arseniyadis

  DOI：10.1021/acs.orglett.0c02079

  日期：2020.8.7

  A highly enantioselective synthesis of alpha-branched acrylonitriles is reported featuring a one-pot sequential asymmetric Michael addition/retro-Dieckmann/retro-Michael fragmentation cascade. The method, which relies on a solid, bench-stable, and commercially available acrylonitrile surrogate, is practical, scalable, and highly versatile and provides a direct access to a wide range of enantioenriched nitrite-containing building blocks. Most importantly, the method offers a new tool to incorporate an acrylonitrile moiety in an asymmetric fashion.
• A General Strategy for the Synthesis of Truxinate Natural Products Enabled by Enantioselective [2+2] Photocycloadditions
  作者：Matthew J. Genzink、Matthew D. Rossler、Herman Recendiz、Tehshik P. Yoon

  DOI：10.1021/jacs.3c07132

  日期：2023.9.6

  Pseudodimeric cyclobutanes constitute a large class of natural products that could, in principle, be efficiently synthesized via [2+2] photocycloadditions. However, the difficulty in developing chemo-, regio-, diastereo-, and enantioselective cycloadditions has limited their use in asymmetric syntheses. Herein, we show that chiral acid catalysts promote highly selective visible-light photocycloadditions

  伪二聚环丁烷构成一大类天然产物，原则上可以通过[2+2]光环加成有效合成。然而，开发化学选择性、区域选择性、非对映选择性和对映选择性环加成的困难限制了它们在不对称合成中的应用。在此，我们证明手性酸催化剂促进高选择性可见光光环加成，其产物可以快速转化为truxinate天然产物。这种通用方法能够合成具有优异对映选择性的二聚体和假二聚体环丁烷天然产物。