(R)-methyl 2-[(4-cyanophenyl)(hydroxy)methyl]acrylate | 1341212-09-6

• 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: (R)-methyl 2-[(4-cyanophenyl)(hydroxy)methyl]acrylate
• 英文别名: methyl (R)-2-[(4-cyanophenyl)(hydroxy)methyl]acrylate；methyl 2-[(R)-(4-cyanophenyl)-hydroxymethyl]prop-2-enoate
• CAS: 1341212-09-6
• 化学式: C₁₂H₁₁NO₃
• 分子量: 217.224
• InChiKey: OXUUXKRFIZARSK-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  70.3
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  丙烯酸甲酯（MA） 、 4-氰基苯甲醛 在 N-[(S)-1-(diphenylphosphanyl)-3-methylbutan-2-yl]-N’-(2,3,4,6-tetra-O-methyl-β-D-glucopyranosyl)thiourea 作用下， 以 甲基叔丁基醚 为溶剂， 反应 24.25h， 以84% ee的产率得到
  参考文献：
  名称：

  d-葡萄糖和α-氨基酸衍生的双功能（硫）脲-膦有机催化剂及其在对映选择性 Morita-Baylis-Hillman 反应中的应用

  摘要：

  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。

  DOI：

  10.1055/s-0035-1560931

文献信息

• 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。
• Organocatalyzed Baylis–Hillman reaction: an enantioselective approach
  作者：Prashant B. Thorat、Santosh V. Goswami、Bhimrao C. Khade、Sudhakar R. Bhusare

  DOI：10.1016/j.tetasy.2012.08.013

  日期：2012.9

  A convenient protocol has been developed for the synthesis of Baylis-Hillman adducts in the presence of a base and an organocatalyst. We have designed and synthesized organocatalysts based on hydrogen bonding using a pyrrolidine ring as the backbone and applied them to Baylis-Hillman transformations. This method provides products in good to high yields (73-90%) and with excellent enantiomeric excesses (up to 96%) and reasonable reaction times. (C) 2012 Elsevier Ltd. All rights reserved.
• 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。