(S)-(+)-methyl 3-hydroxy-2-methylene-3-(3-chlorophenyl)propanoate | 1238053-90-1

• 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: (S)-(+)-methyl 3-hydroxy-2-methylene-3-(3-chlorophenyl)propanoate
• 英文别名: (S)-methyl 2-((3-chlorophenyl)(hydroxy)methyl)acrylate；methyl 2-[(S)-(3-chlorophenyl)-hydroxymethyl]prop-2-enoate
• CAS: 1238053-90-1
• 化学式: C₁₁H₁₁ClO₃
• 分子量: 226.66
• InChiKey: ZZOVVJBYLKLRCC-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  46.53
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  methyl 2-[(S)-(3-chlorophenyl)-(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 3-hydroxy-2-methylene-3-(3-chlorophenyl)propanoate
  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

• 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.