methyl (R)-3-(4-chlorophenyl)-3-hydroxy-2-methylenepropanoate

• 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 (R)-3-(4-chlorophenyl)-3-hydroxy-2-methylenepropanoate
• 英文别名: (R)-methyl 2-((4-chlorophenyl)(hydroxy)methyl)acrylate；(R)-methyl 2-[(4-chlorophenyl)(hydroxy)methyl]acrylate；methyl (R)-2-[(4-chlorophenyl)(hydroxy)methyl]acrylate；methyl 2-[(R)-(4-chlorophenyl)-hydroxymethyl]prop-2-enoate
• 化学式: C₁₁H₁₁ClO₃
• mdl: MFCD09030953
• 分子量: 226.66
• InChiKey: GBKHNNKNMGBHSY-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 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：
  3

反应信息

• 作为反应物：
  描述：

  methyl (R)-3-(4-chlorophenyl)-3-hydroxy-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68%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：

  4-氯苯甲醛 、 丙烯酸甲酯（MA） 在 三乙烯二胺 作用下， 以 neat (no solvent) 为溶剂， 反应 120.0h， 以94%的产率得到methyl (R)-3-(4-chlorophenyl)-3-hydroxy-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

• Enantioselective Synthesis of the Optically Active α-Methylene-β-hydroxy Esters, Equivalent Compounds to Morita−Baylis−Hillman Adducts, Using Successive Asymmetric Aldol Reaction and Oxidative Deselenization
  作者：Isamu Shiina、Yu-suke Yamai、Takahisa Shimazaki

  DOI：10.1021/jo051276y

  日期：2005.9.1

  The asymmetric aldol reaction of a tetra-substituted ketene silyl acetal including an alkylseleno group with aldehydes has been developed by the promotion of Sn(OTf)2 coordinated with a chiral diamine to afford the corresponding aldols having chiral quaternary centers at the α-positions. The facile oxidative deselenization of these aldol compounds produces optically active α-methylene-β-hydroxy esters

  通过促进与手性二胺配位的Sn（OTf）2得到相应的具有在α-位的手性季中心的醛醇，已经开发了包括烷基硒烯基的四取代的乙烯酮甲硅烷基乙缩醛与醛的不对称醛醇缩合反应。这些羟醛化合物的轻度氧化脱硒作用产生旋光性α-亚甲基-β-羟基酯，它们对应于由不对称Morita-Baylis-Hillman反应制备的加合物。
• 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。
• A New Dual Catalytic System for Asymmetric Morita-Baylis-Hillman Reaction
  作者：Jürgen Liebscher、Jabbar Shah、Zekarias Yacob、Alexander Bunge

  DOI：10.1055/s-0030-1258531

  日期：2010.9

  High yields and enantioselectivities up to 88% were achieved in asymmetric Morita-Baylis-Hillman reactions using a combination of chiral amino acid derived guanidines and triphenylphosphane as a novel dual catalytic system.

  在不对称 Morita-Baylis-Hillman 反应中使用手性氨基酸衍生的胍和三苯基膦的组合作为新型双催化系统实现了高产率和高达 88% 的对映选择性。