methyl (S)-2-[(4-bromophenyl)(hydroxy)methyl]acrylate | 1255700-18-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl (S)-2-[(4-bromophenyl)(hydroxy)methyl]acrylate
• 英文别名: methyl 2-((4-bromophenyl)(hydroxy)methyl)acrylate；methyl (S)-2-((4-bromophenyl)(hydroxyl)methyl)acrylate；(S)-methyl 2-((4-bromophenyl)(hydroxy)methyl)acrylate；methyl 2-[(S)-(4-bromophenyl)-hydroxymethyl]prop-2-enoate
• CAS: 1255700-18-5
• 化学式: C₁₁H₁₁BrO₃
• 分子量: 271.111
• InChiKey: MWGGZHVZWMWMRW-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对溴苯甲醛 、 丙烯酸甲酯（MA） 在 1-((1R,2R)-1-((tert-butyldimethylsilyl)oxy)-3-(di-o-tolylphosphanyl)-1-phenylpropan-2-yl)-3-phenylthiourea 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以90%的产率得到methyl (S)-2-[(4-bromophenyl)(hydroxy)methyl]acrylate
  参考文献：
  名称：

  不对称Morita–Baylis–Hillman反应：基于质谱反向反应筛选的催化剂开发和机理研究

  摘要：

  建立了评估不对称森田-贝利斯-希尔曼（MBH）反应催化剂的有效方案。通过对映异构体MBH产物的质谱反向反应筛选，发现一种有效的双功能膦催化剂在丙烯酸甲酯与醛类的MBH反应中性能优于文献中已知的催化剂。正反反应的选择性与动力学测量之间的紧密匹配提供了有力的证据，表明醛醇缩合步骤而不是随后的质子转移是速率和对映选择性的决定因素。

  DOI：

  10.1002/chem.201604616

文献信息

• Bifunctional (Thio)urea–Phosphine Organocatalysts Derived from d-Glucose and α-Amino Acids and Their Application to the Enantio­selective Morita–Baylis–Hillman Reaction
  作者：J. Veselý、I. Gergelitsová、J. Tauchman、I. Císařová

  DOI：10.1055/s-0035-1560931

  日期：——

  Novel (thio)urea–tertiary phosphines were developed for use as bifunctional organocatalysts readily available from naturally occurring molecules: saccharides and amino acids. The efficiency of the organocatalysts was demonstrated in the asymmetric Morita–Baylis–Hillman (MBH) reaction of aromatic aldehydes with acrylates. The MBH products were obtained in good yields (up to 85%) and with high enantioselectivities

  新型（硫）脲-叔膦被开发用作双功能有机催化剂，这些催化剂很容易从天然存在的分子中获得：糖类和氨基酸。在芳香醛与丙烯酸酯的不对称 Morita-Baylis-Hillman (MBH) 反应中证明了有机催化剂的效率。MBH 产品以良好的产率（高达 85%）和高对映选择性（高达 87% ee）获得。
• Enantioselective Morita–Baylis–Hillman reaction promoted by l-threonine-derived phosphine–thiourea catalysts
  作者：Xiaoyu Han、Youqing Wang、Fangrui Zhong、Yixin Lu

  DOI：10.1039/c1ob05881a

  日期：——

  A series of bifunctional phosphine–thiourea organic catalysts based on natural amino acid scaffolds were designed and prepared. L-Threonine-derived bifunctional phosphine catalysts were found to be very efficient in promoting asymmetric Morita–Baylis–Hillman (MBH) reaction of acrylates with aromatic aldehydes, affording the desired MBH adducts with up to 90% ee. To gain mechanistic insights into the reaction, the effects of adding various additives on the MBH reaction were investigated. We propose that the hydrogen bonding interactions between the thiourea moiety of the catalyst and the enolate intermediate are crucial for the stereochemical outcome of the reaction. The method described in this report may provide a practical solution to the enantioselective MBH reaction of simple acrylates.

  我们设计并制备了一系列基于天然氨基酸支架的双功能膦硫脲有机催化剂。研究发现，L-苏氨酸衍生的双功能膦催化剂在促进丙烯酸酯与芳香醛的不对称莫里塔-贝利斯-希尔曼（MBH）反应方面非常有效，可以得到所需的 MBH 加合物，ee 值高达 90%。为了深入了解该反应的机理，我们研究了添加各种添加剂对 MBH 反应的影响。我们认为，催化剂的硫脲分子与烯醇中间体之间的氢键相互作用对反应的立体化学结果至关重要。本报告所述方法可为简单丙烯酸酯的对映选择性 MBH 反应提供实用的解决方案。
• A New Dual Catalytic System for Asymmetric Morita-Baylis-Hillman Reaction
  作者：Jürgen Liebscher、Jabbar Shah、Zekarias Yacob、Alexander Bunge

  DOI：10.1055/s-0030-1258531

  日期：2010.9

  High yields and enantioselectivities up to 88% were achieved in asymmetric Morita-Baylis-Hillman reactions using a combination of chiral amino acid derived guanidines and triphenylphosphane as a novel dual catalytic system.

  在不对称 Morita-Baylis-Hillman 反应中使用手性氨基酸衍生的胍和三苯基膦的组合作为新型双催化系统实现了高产率和高达 88% 的对映选择性。
• <i>P</i>-Stereogenic β-Aminophosphines: Preparation and Applications in Enantioselective Organocatalysis
  作者：Hsin Y. Su、Mark S. Taylor

  DOI：10.1021/acs.joc.7b00199

  日期：2017.3.17

  configuration at phosphorus, is a key step in this process. The products obtained are new building blocks for the synthesis of P-chiral ligands and organocatalysts. In a proof-of-concept application in organocatalysis, the diastereomeric P-chiral β-aminophosphine-based bifunctional thioureas displayed significantly different activities in the Morita–Baylis–Hillman reaction of methyl acrylate with benzaldehyde

  描述了具有基于碳和磷的手性中心的立体定义的β-氨基膦的合成。该方法涉及拆分通过氨基醇衍生的环状氨基磺酸酯的开环获得的β-氨基氧化膦非对映异构体的混合物。立体定向，硼烷促进的β-氨基膦氧化物还原是在该过程中的关键步骤，该还原反应在温和条件下发生并且磷的构型反转。获得的产物是合成P-手性配体和有机催化剂的新组成部分。在有机催化的概念验证应用中，非对映体P-手性β-氨基膦基双官能硫脲在丙烯酸甲酯与苯甲醛衍生物的Morita-Baylis-Hillman反应中显示出明显不同的活性。
• Asymmetric Morita-Baylis-Hillman Reaction: Catalyst Development and Mechanistic Insights Based on Mass Spectrometric Back-Reaction Screening
  作者：Patrick G. Isenegger、Florian Bächle、Andreas Pfaltz

  DOI：10.1002/chem.201604616

  日期：2016.12.5

  Morita–Baylis–Hillman (MBH) reaction was developed. By mass spectrometric back‐reaction screening of quasi‐enantiomeric MBH products, an efficient bifunctional phosphine catalyst was identified that outperforms literature‐known catalysts in the MBH reaction of methyl acrylate with aldehydes. The close match between the selectivities measured for the forward and back reaction and kinetic measurements provided

  建立了评估不对称森田-贝利斯-希尔曼（MBH）反应催化剂的有效方案。通过对映异构体MBH产物的质谱反向反应筛选，发现一种有效的双功能膦催化剂在丙烯酸甲酯与醛类的MBH反应中性能优于文献中已知的催化剂。正反反应的选择性与动力学测量之间的紧密匹配提供了有力的证据，表明醛醇缩合步骤而不是随后的质子转移是速率和对映选择性的决定因素。