(R)-(-)-5-ethoxycarbonyl-6-methyl-4-(2-chlorophenyl)-3,4-dihydropyrimidin-2(1H)-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (R)-(-)-5-ethoxycarbonyl-6-methyl-4-(2-chlorophenyl)-3,4-dihydropyrimidin-2(1H)-one
• 英文别名: ethyl (S)-4-(2-chlorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate；(S)-5-ethoxycarbonyl-6-methyl-4-(2-chlorophenyl)-3,4-dihydropyrimidin-2(1H)-one；ethyl (4S)-4-(2-chlorophenyl)-6-methyl-2-oxo-3,4-dihydro-1H-pyrimidine-5-carboxylate
• 化学式: C₁₄H₁₅ClN₂O₃
• 分子量: 294.738
• InChiKey: BAKBIOFRSIUKMG-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  67.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  ethyl 6-methyl-2-oxo-4-(2-chloro)-phenyl-3,4-dihydropyrimidine-5-carboxylate 在 chiral silica-based resin 、 溶剂黄146 作用下， 以 正己烷 、 异丙醇 为溶剂， 生成 (R)-(-)-5-ethoxycarbonyl-6-methyl-4-(2-chlorophenyl)-3,4-dihydropyrimidin-2(1H)-one 、 (S)-(+)-5-ethoxycarbonyl-6-methyl-4-(2-chlorophenyl)-3,4-dihydropyrimidin-2(1H)-one
  参考文献：
  名称：

  The enantiomeric recognition of dihydropyrimidonic compounds by chiral selectors derived from 4- or 2-chloro-3,5-dinitrobenzoic acid

  摘要：

  Six new chiral packing materials for high performance liquid chromatography have been prepared from chiral selectors consisting of 4- or 2-chloro-3,5-dinitrobenzoic acid, L-alanine and different pi-donor aromatic units. Comparative tests of these newly prepared CSPs on separation efficiency for 13 racemic dihydropyrimidonic (DHPM) analytes have revealed the strong contribution of the pi-acceptor branching unit, as well as the important influence of the structure of the terminal pi-donor unit. The role of the terminal aromatic group is primarily to increase the rigidity of the selector structure. Comparisons of the data revealed that selectors bound on the silica gel could be preorganized during the process of chiral recognition, resulting in the similar enantioseparation properties for DHPM analytes on both types of CSPs. However, some other compounds, such as amino alcohol beta-agonists, exhibit very different enantioseparations. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.01.042

文献信息

• Towards Enzyme-like, Sustainable Catalysis: Switchable, Highly Efficient Asymmetric Synthesis of Enantiopure Biginelli Dihydropyrimidinones or Hexahydropyrimidinones
  作者：V. J. Lillo、J. M. Saá

  DOI：10.1002/chem.201604433

  日期：2016.11.21

  Organocatalysts displaying a network of cooperative hydrogen bonds (NCHB) have been employed in an enzyme‐like manner for a direct, switchable synthesis of enantiopure hexahydropyrimidinones (HHPMs) or dihydropyrimidinones (DHPMs), which starts at a common, easily accessible α‐ureidosulfone stage. The NCHB organocatalyst exploits all its potential as a pure hydrogen‐bond biomimetic catalyst even in

  具有协同氢键网络（NCHB）的有机催化剂已以类似酶的方式用于直接，可转换的对映纯六氢嘧啶酮（HHPM）或二氢嘧啶酮（DHPM）的合成，其起始于常见的易于获得的α-脲基砜阶段。NCHB有机催化剂即使在存在有机碱的情况下，也可以发挥其作为纯氢键仿生催化剂的全部潜力。这种单锅，非对映和对映选择性合成方法已被证明是可靠，可扩展，高效且对环境无害的。首次报道了一种直接，真正实用的对映纯HHPMs。
• Highly Enantioseletive Biginelli Reaction Using a New Chiral Ytterbium Catalyst:  Asymmetric Synthesis of Dihydropyrimidines
  作者：Yijun Huang、Fengyue Yang、Chengjian Zhu

  DOI：10.1021/ja056092f

  日期：2005.11.30

  enantioselective three-component Biginelli condensation catalyzed by a recyclable chiral ytterbium triflate with a novel hexadentate amine phenol ligand containing a pyridyl group has been developed. A wide range of optically active dihydropyrimidines with remarkable pharmacological interest was obtained in high yields with good to excellent enantioselectivities under mild conditions.

  已开发出由可回收的手性三氟甲磺酸镱与含有吡啶基的新型六齿胺苯酚配体催化的高对映选择性三组分 Biginelli 缩合反应。在温和条件下以高产率获得了具有显着药理学意义的多种旋光二氢嘧啶，具有良好到优异的对映选择性。
• Bifunctional primary amine-thiourea–TfOH (BPAT·TfOH) as a chiral phase-transfer catalyst: the asymmetric synthesis of dihydropyrimidines
  作者：Yangyun Wang、Jipan Yu、Zhiwei Miao、Ruyu Chen

  DOI：10.1039/c0ob01268h

  日期：——

  An enantioselective Biginelli reaction has been developed by using a bifunctional primary amine-thiourea–TfOH (BPAT·TfOH) as a chiral phase-transfer catalyst and t-BuNH2·TFA as an additive in saturated brine at room temperature. The corresponding dihydropyrimidines were obtained in moderate-to-good yields with up to 99% ee under mild conditions. A plausible transition state has been proposed to explain the origin of the activation and the asymmetric induction.

  在室温饱和盐水中，使用双功能伯胺-硫脲-TfOH（BPATÂ-TfOH）作为手性相转移催化剂和 t-BuNH2Â-TFA 作为添加剂，开发了一种对映体选择性 Biginelli 反应。在温和的条件下，得到了相应的二氢嘧啶，收率从中等到良好，ee高达 99%。研究人员提出了一种可信的过渡态来解释活化和不对称诱导的起源。
• ACCESS TO CHIRAL BISPHENOL (BPOL) LIGANDS THROUGH DESYMMETRIZING ASYMMETRIC ORTHO-SELECTIVE MONO-HALOGENATION
  申请人：The Chinese University of Hong Kong

  公开号：US20210300853A1

  公开（公告）日：2021-09-30

  The subject invention pertains to a method of halogenating phenols, yielding a range of halogenated phenols with enantiomeric ratio of up to 99.5:0.5. In certain embodiments, the subject invention pertains to a method of asymmetric halogenation of bisphenol, yielding a range of chiral bisphenol ligands. The novel chiral bisphenols are potent privileged catalyst cores that can be applied to the preparation of ligands for various catalytic asymmetric reactions. The catalyst library can easily be accessed because late-stage modification of the scaffold can readily be executed through cross-coupling of the halogen handles on the bisphenols.

  本发明涉及一种卤代酚的卤代方法，可产生范围广泛的卤代酚，其对映比可高达99.5:0.5。在某些实施例中，本发明涉及一种不对称卤代双酚的方法，可产生一系列手性双酚配体。新型手性双酚是有效的特权催化剂核心，可应用于各种催化不对称反应的配体制备。因为可以通过交叉偶联双酚上的卤素手柄进行骨架的后期修饰，所以可以轻松地访问催化剂库。
• Cooperative and Enantioselective NbCl5/Primary Amine Catalyzed Biginelli Reaction
  作者：Yong-Feng Cai、Hua-Meng Yang、Li Li、Ke-Zhi Jiang、Guo-Qiao Lai、Jian-Xiong Jiang、Li-Wen Xu

  DOI：10.1002/ejoc.201000894

  日期：2010.9

  evaluated in the Lewis acid/organocatalysts-based cooperative catalytic Biginelli reaction, which resulted in the determination of a novel cooperative Lewis acid/primary amine catalyst system, NbCl5/QN-NH2. The synergistic effect of NbCl5 and the quinine-derived primary amine is pronounced and gave dihydropyrimidiones (DHPMs) in moderate to good enantioselectivities (up to 84 % ee) and good to excellent yields

  在基于路易斯酸/有机催化剂的协同催化 Biginelli 反应中评估了一系列手性有机催化剂和路易斯酸，从而确定了一种新型的路易斯酸/伯胺协同催化剂体系 NbCl5/QN-NH2。NbCl5 和奎宁衍生的伯胺的协同作用是显着的，在温和的条件下以中等至良好的对映选择性（高达 84% ee）和良好至极好的产率（产率高达 99%）得到二氢嘧啶酮 (DHPM)。