(S)-methyl 2-((4-fluorophenyl)(hydroxy)methyl)acrylate | 1238053-85-4

• 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: (S)-methyl 2-((4-fluorophenyl)(hydroxy)methyl)acrylate
• 英文别名: methyl (S)-2-[(4-fluorophenyl)(hydroxy)methyl]acrylate；methyl 2-((4-fluorophenyl)(hydroxy)methyl)acrylate；(S)-(+)-methyl 3-hydroxy-2-methylene-3-(4-fluorophenyl)propanoate；methyl 2-[(S)-(4-fluorophenyl)-hydroxymethyl]prop-2-enoate
• CAS: 1238053-85-4
• 化学式: C₁₁H₁₁FO₃
• 分子量: 210.205
• InChiKey: YNCNIARQQCBRFC-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 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：
  4

反应信息

• 作为反应物：
  描述：

  (S)-methyl 2-((4-fluorophenyl)(hydroxy)methyl)acrylate 、 (R)-4-bromo-N-(1-phenylethyl)-N-(phenylethynyl)benzenesulfonamide 在 yttrium(III) trifluoromethanesulfonate 作用下， 以 氯苯 为溶剂， 反应 3.0h， 以81.818%的产率得到
  参考文献：
  名称：

  钇催化的串联分子间氢烷氧基化/克莱森重排

  摘要：

  已经开发出有效的钇催化的串联分子间加氢烷氧基化/克莱森重排，以通常良好至优异的产率提供各种γ，δ-不饱和酰胺。重要的是，获得了高的Z / E选择性和非对映选择性。该方法的其他显着特征包括可广泛使用的底物，与各种官能团的相容性以及温和的反应条件。

  DOI：

  10.1021/acs.joc.7b01612
• 作为产物：
  描述：

  methyl 2-[(S)-(4-fluorophenyl)-(3-phenylpentan-3-ylperoxy)methyl]prop-2-enoate 在 锌 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 3.0h， 生成 (S)-methyl 2-((4-fluorophenyl)(hydroxy)methyl)acrylate
  参考文献：
  名称：

  有机催化过氧不对称烯丙基烷基化†

  摘要：

  改性的金鸡纳生物碱（高达93％ee）催化了森田-贝利斯-希尔曼碳酸盐与氢过氧烷烃的过氧不对称烯丙基烷基化反应，可以有效地衍生出手性α-亚甲基-β-羟基酯。

  DOI：

  10.1039/b912110b

文献信息

• 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。
• 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。
• Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water
  作者：Bo Zhu、Lin Yan、Yuanhang Pan、Richmond Lee、Hongjun Liu、Zhiqiang Han、Kuo-Wei Huang、Choon-Hong Tan、Zhiyong Jiang

  DOI：10.1021/jo201096e

  日期：2011.8.19

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.