苯丙酸,b-羟基-a-亚甲基-,甲基酯,(R)- | 18020-59-2

• 物质功能分类: 医药中间体 - 原料药中间体
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 中文名称: 苯丙酸,b-羟基-a-亚甲基-,甲基酯,(R)-
• 英文名称: methyl (S)-3-hydroxy-3-phenyl-2-methylenepropanoate
• 英文别名: (S)-(+)-methyl 3-hydroxy-2-methylene-3-phenylpropanoate；(S)-2-(hydroxyphenylmethyl)acrylic acid methyl ester；methyl (S)-3-hydroxy-2-methylene-3-phenylpropanoate；(S)-(+)-methyl 2-[hydroxy(phenyl)methyl]acrylate；methyl (S)-2-(hydroxyl(phenyl)methyl)acrylate；(S)-methyl 2-(hydroxy(phenyl)methyl)acrylate；(+)Methyl 3(S)-hydroxy-2-methylene-3-phenylpropanoate；methyl 2-[(S)-hydroxy(phenyl)methyl]prop-2-enoate
• CAS: 18020-59-2；98837-37-7；140630-33-7；108945-27-3
• 化学式: C₁₁H₁₂O₃
• 分子量: 192.214
• InChiKey: VZGOKIHNKHAORQ-SNVBAGLBSA-N

物化性质

• 熔点：
  126-128 °C
• 沸点：
  103-105 °C(Press: 0.1 Torr)
• 密度：
  1.141±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 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

安全信息

• 海关编码：
  2918199090

反应信息

• 作为反应物：
  描述：

  苯丙酸,b-羟基-a-亚甲基-,甲基酯,(R)- 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 C₁₉H₂₄N₂O₂ 作用下， 以 甲醇 、 二氯甲烷 、 甲基叔丁基醚 为溶剂， 反应 20.0h， 生成 tert-butyl 3-methyl-2-oxo-4-phenyl-3,4,5,9b-tetrahydroindeno[1,2-b]pyran-4a(2H)-carboxylate
  参考文献：
  名称：

  β-酮基酯对MBH碳酸酯的有机催化对映选择性烯丙基烷基化†

  摘要：

  描述了由β-ICD催化的Morita-Baylis-Hillman碳酸盐与β-酮酸酯的高度立体选择性烯丙基烷基化。得到具有两个高的非对映选择性（高达10∶1dr）和对映选择性（高达95％ee）的高产率的含有两个相邻的季碳和叔碳中心的相应产物。

  DOI：

  10.1039/c4ob00682h
• 作为产物：
  描述：

  methyl 2-{[(tert-butoxycarbonyl)oxy](phenyl)methyl}acrylate 在 calcium fluoride 、 水 、 hydroquinidine (anthraquinone-1,4-diyl) diether 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 72.0h， 以86%的产率得到苯丙酸,b-羟基-a-亚甲基-,甲基酯,(R)-
  参考文献：
  名称：

  Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water

  摘要：

  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.

  DOI：

  10.1021/jo201096e

文献信息

• Substituted piperidine compounds and methods of their use
  申请人：Dolle Ellwood Roland

  公开号：US20050203123A1

  公开（公告）日：2005-09-15

  Certain 4-aryl-piperidine compounds, including N-substituted 9β-substituted-5-(3-substituted-phenyl)morphans and N-substituted octahydro-4a-(3-hydroxyphenyl)-10a-methyl-benzo[g]isoquinolines, pharmaceutical compositions, and methods of their use, inter alia, as opioid antagonists are disclosed.

  某些4-芳基哌啶化合物，包括N-取代的9β-取代-5-(3-取代-苯基)吗啡烷和N-取代的八氢-4a-(3-羟基苯基)-10a-甲基-苯并[g]异喹啉，以及包含它们的药物组合物和用途，例如作为阿片类药物拮抗剂，被披露。
• A chiral squaramide-catalyzed asymmetric dearomative tandem annulation reaction through a kinetic resolution of MBH alcohols: highly enantioselective synthesis of three-dimensional heterocyclic compounds
  作者：Leijie Zhou、Yuan Zeng、Xing Gao、Qijun Wang、Chang Wang、Bo Wang、Wei Wang、Yongjun Wu、Bing Zheng、Hongchao Guo

  DOI：10.1039/c9cc05483a

  日期：——

  dearomative tandem annulation reaction of unmodified Morita–Baylis–Hillman alcohols with azomethine imines has been achieved through a kinetic resolution of MBH alcohols under mild conditions, giving pharmaceutically interesting functionalized hetero-bicyclo[3.3.1]nonane derivatives in good to excellent yields with excellent enantioselectivities.

  在这种交流中，通过温和条件下MBH醇的动力学拆分，实现了未修饰的Morita-Baylis-Hillman醇与偶氮甲亚胺的手性方酸酰胺催化的不对称脱芳香性串联环化反应，得到了药学上有意义的官能化杂双环[3.3.1] ]壬烷衍生物，具有良好的至优异的产率和优异的对映选择性。
• Chiral Lewis Acid-Catalyzed Asymmetric Baylis−Hillman Reactions
  作者：Kung-Shuo Yang、Wei-Der Lee、Jia-Fu Pan、Kwunmin Chen

  DOI：10.1021/jo026318m

  日期：2003.2.1

  acid-catalyzed asymmetric Baylis-Hillman reaction is described. Good to high enantioselectivities were obtained using 3 mol % chiral catalyst. Novel camphor-derived dimerized ligands were prepared from the condensation of (+)-ketopinic acid with the corresponding diamines and hydrazine under acidic conditions. When alpha-naphthyl acrylate was used as a Michael acceptor, the reaction is complete within

  描述了有效的手性路易斯酸催化的不对称Baylis-Hillman反应。使用3mol％的手性催化剂获得良好至高的对映选择性。由（+）-酮酸与相应的二胺和肼在酸性条件下的缩合反应制得了新的樟脑衍生的二聚配体。当使用丙烯酸α-萘基酯作为迈克尔受体时，反应在20分钟内以高的立体选择性和合理的化学收率完成。
• Chiral cheating agent and chiral catlyst
  申请人：——

  公开号：US20040176243A1

  公开（公告）日：2004-09-09

  Chiral chelating agents and chiral catalysts, which are formed from the chiral chelating agents and metal, are described. One chiral chelating agent has a general formula (1) as illustrated below: 1 wherein R represents H, methyl, ethyl, a primary, secondary or tertiary straight, branched or cyclic alkyl group having 3-7 carbon atoms, a heterocyclic or aromatic group, an aromatic group substituted at the 2-, 3- or 4-position, an aromatic-like group, or a naphthyl or naphthyl-derived group, and n is an integer between 0 and 4.

  手性螯合剂和手性催化剂是由手性螯合剂和金属形成的。其中一种手性螯合剂具有如下所示的一般式（1）： 1 其中R代表H、甲基、乙基、具有3-7个碳原子的一级、二级或三级直链、支链或环烷基基团、杂环或芳香基团、在2-、3-或4-位取代的芳香基团、类芳香基团，或者萘基或萘基衍生基团，n为0到4之间的整数。
• Asymmetric synthesis of multifunctional aryl allyl ethers by nucleophilic catalysis
  作者：Shuai Zhao、Lei Jin、Zhi-Li Chen、Xue Rui、Jia-Yi He、Ran Xia、Ke Chen、Xiang-Xiang Chen、Zi-Jian Yin、Xin Chen

  DOI：10.1039/c9ra00155g

  日期：——

  Asymmetric allylic substitution of Morita–Baylis–Hillman (MBH) carbonates with less-nucleophilic phenols mediated by nucleophilic amine catalysis was successfully developed. A variety of substituted aryl allyl ethers were afforded with moderate to high yields with excellent enantioselectivities. The chiral MBH alcohol could be easily accessed from the corresponding aryl allyl ether.

  成功开发了由亲核胺催化介导的低亲核酚类对 Morita-Baylis-Hillman (MBH) 碳酸酯的不对称烯丙基取代。以中等至高产率和优异的对映选择性提供了多种取代的芳基烯丙基醚。手性 MBH 醇可以很容易地从相应的芳基烯丙基醚中获得。