methyl 3-hydroxy-3-(2-nitrophenyl)-2-methylenepropanoate | 871361-24-9

• 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 3-hydroxy-3-(2-nitrophenyl)-2-methylenepropanoate
• 英文别名: (R)-methyl 2-((2-nitrophenyl)(hydroxy)methyl)acrylate；(R)-methyl 2-(hydroxy(2-nitrophenyl)methyl)acrylate；methyl (R)-2-[hydroxy(2-nitrophenyl)methyl]acrylate；methyl 2-[(R)-hydroxy-(2-nitrophenyl)methyl]prop-2-enoate
• CAS: 871361-24-9
• 化学式: C₁₁H₁₁NO₅
• 分子量: 237.212
• InChiKey: QYEGBSLVNHSHFX-JTQLQIEISA-N

物化性质

• 沸点：
  406.0±45.0 °C(Predicted)
• 密度：
  1.316±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 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：
  92.4
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3-hydroxy-3-(2-nitrophenyl)-2-methylenepropanoate 在 叔丁基过氧化氢 、 甲基锂 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 以66%的产率得到
  参考文献：
  名称：

  Study of the stereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters

  摘要：

  The diastereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters has been studied. The 3-hydroxy-2-methylene esters were obtained through a Morita-Baylis-Hillman reaction. The resulting epoxyesters were treated with thiophenol for transformation into 2,3-dihydroxy-2-((phenylthio)methyl), which upon treatment with triphosgene afforded the corresponding cyclic carbonates. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.11.014
• 作为产物：
  描述：

  丙烯酸甲酯（MA） 、 邻硝基苯甲醛 在 三乙烯二胺 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 16.0h， 以95%的产率得到methyl 3-hydroxy-3-(2-nitrophenyl)-2-methylenepropanoate
  参考文献：
  名称：

  Study of the stereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters

  摘要：

  The diastereoselectivity of the nucleophilic epoxidation of 3-hydroxy-2-methylene esters has been studied. The 3-hydroxy-2-methylene esters were obtained through a Morita-Baylis-Hillman reaction. The resulting epoxyesters were treated with thiophenol for transformation into 2,3-dihydroxy-2-((phenylthio)methyl), which upon treatment with triphosgene afforded the corresponding cyclic carbonates. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.11.014

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。
• TiO₂@UiO-68-CIL: A Metal–Organic-Framework-Based Bifunctional Composite Catalyst for a One-Pot Sequential Asymmetric Morita–Baylis–Hillman Reaction
  作者：Yu-Hong Hu、Cong-Xue Liu、Jian-Cheng Wang、Xiu-Hui Ren、Xuan Kan、Yu-Bin Dong

  DOI：10.1021/acs.inorgchem.8b02132

  日期：2019.4.15

  TiO2@UiO-68-CIL (2) was prepared by impregnating 1 in a toluene solution of Ti(OPri)4 and sequential in situ hydrolysis. The obtained 2 can be a bifunctional asymmetric heterogeneous catalyst to successfully promote the one-pot Morita–Baylis–Hillman reaction starting from aromatic alcohols in a tandem way.

  通过新型预改性手性化合物的组合成功制备了由1-吡咯烷-2--2-咪唑修饰的手性UiO-68型金属有机骨架UiO-68-CIL（1）的手性离子液体（CIL）部分。CIL配体（H 2 L-CIL）和ZrCl 4通过溶剂热法。在TiO 2 -loaded的TiO 2 @ UIO-68-CIL（2）通过浸渍制备1中的Ti的甲苯溶液（OPR我）4和顺序原位水解。获得2 可以是双功能不对称多相催化剂，可以成功地从芳香族醇开始串联促进一锅森田-贝利斯-希尔曼反应。
• 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。
• 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。