tert-butyl (R)-2-[hydroxy(4-nitrophenyl)methyl]acrylate | 114106-91-1

• 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: tert-butyl (R)-2-[hydroxy(4-nitrophenyl)methyl]acrylate
• 英文别名: tert-butyl 2-[(R)-hydroxy-(4-nitrophenyl)methyl]prop-2-enoate
• CAS: 114106-91-1
• 化学式: C₁₄H₁₇NO₅
• 分子量: 279.293
• InChiKey: OITZZQPGNBSYIS-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  92.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  丙烯酸叔丁酯 、 对硝基苯甲醛 在 1-((2S,3R)-3-(tert-butyldimethylsilyloxy)-1-(diphenylphosphino)butan-2-yl)-3-(4-fluorophenyl)thiourea 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 tert-butyl (R)-2-[hydroxy(4-nitrophenyl)methyl]acrylate 、 tert-butyl (S)-2-[hydroxy(4-nitrophenyl)methyl]acrylate
  参考文献：
  名称：

  Enantioselective Morita–Baylis–Hillman reaction promoted by l-threonine-derived phosphine–thiourea catalysts

  摘要：

  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。

  DOI：

  10.1039/c1ob05881a

文献信息

• Enantioselective Morita-Baylis-Hillman Reaction Organocatalyzed by Glucose-based Phosphinothiourea
  作者：Weihong Yang、Feng Sha、Xin Zhang、Kui Yuan、Xinyan Wu

  DOI：10.1002/cjoc.201200740

  日期：2012.9.27

  A class of bifunctional phosphinothioureas derived from saccharide was developed as new organocatalysts for the enantioselective Morita‐Baylis‐Hillman reaction between acrylates and aldehydes. With 10 mol% of glucose‐based phosphinothiourea 1d, the allylic alcohols were obtained in up to 96% yield and 83% ee under mild reaction conditions.

  一类衍生自糖的双功能膦硫脲被开发为丙烯酸和醛之间对映选择性森田-贝利斯-希尔曼反应的新型有机催化剂。在温和的反应条件下，使用10 mol％的葡萄糖基膦硫脲1d可获得高达96％的收率和83％ee的烯丙醇。
• Chiral phosphinothiourea-catalyzed asymmetric Morita–Baylis–Hillman reactions of acrylates with aromatic aldehydes
  作者：Kui Yuan、Hong-Liang Song、Yinjun Hu、Xin-Yan Wu

  DOI：10.1016/j.tet.2009.07.066

  日期：2009.9

  chiral bifunctional phosphinothioureas were synthesized and applied to the enantioselective Morita–Baylis–Hillman reaction of aromatic aldehydes with acrylates. In the presence of 8 mol % of organocatalyst 2e, the Baylis–Hillman adducts were obtained in good enantioselectivities and up to 96% yield under mild reaction conditions.

  合成了一系列手性双官能硫代硫脲，并将其用于芳香醛与丙烯酸酯的对映选择性森田-贝利斯-希尔曼反应。在8 mol％的有机催化剂2e的存在下，在温和的反应条件下以良好的对映选择性和高达96％的产率获得了Baylis-Hillman加合物。
• 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 of Acrylates with Nitrobenzaldehydes Promoted by the Bifunctional Ferrocene-Based Phosphinothiourea Organocatalysts
  作者：Chuang Li、Peng-Fei Ma、Yang Lei、Hui Chen、Shao-Yu Guan、Ru Jiang、Wei-Ping Chen

  DOI：10.1007/s10562-016-1759-9

  日期：2016.8

  organocatalysts were synthesized and applied to the enantioselective Morita–Baylis–Hillman reaction of acrylates with nitrobenzaldehydes, giving the desired products in up to 99.7 % ee. The strong electron-withdrawing effect of nitro group and hydrogen bonding interactions between the thiourea moiety of catalyst and aldehyde might be crucial during the enantio-controlling process.Graphical Abstract

  合成了一系列基于二茂铁的双功能膦硫脲有机催化剂，并将其应用于丙烯酸酯与硝基苯甲醛的对映选择性 Morita-Baylis-Hillman 反应，得到了高达 99.7% ee 的所需产物。硝基的强吸电子作用和催化剂的硫脲部分与醛之间的氢键相互作用可能在对映体控制过程中起关键作用。
• Valine-derived phosphinothiourea as organocatalyst in enantioselective Morita–Baylis–Hillman reactions of acrylates with aromatic aldehydes
  作者：Jing-Jing Gong、Kui Yuan、Xin-Yan Wu

  DOI：10.1016/j.tetasy.2009.07.047

  日期：2009.9

  A new type of chiral bifunctional phosphinothiourea derived from L-valine is synthesized and used as an organocatalyst in the enantioselective Monta-Baylis-Hillman reaction of aromatic aldehydes with acrylates. The desired products were obtained in good enantioselectivities (up to :33% ee) and in excellent yields (up to 96%) under mild reaction conditions. (C) 2009 Elsevier Ltd All rights reserved