(S)-(+)-5-ethoxycarbonyl-6-methyl-4-(4-methoxyphenyl)-3,4-dihydropyrimidin-2(1H)-one | 1026791-46-7

• 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: (S)-(+)-5-ethoxycarbonyl-6-methyl-4-(4-methoxyphenyl)-3,4-dihydropyrimidin-2(1H)-one
• 英文别名: (S)-5-ethoxycarbonyl-4-(4-methoxyphenyl)-6-methyl-3,4-dihydropyrimidin-2(1H)-one；ethyl (4S)-4-(4-methoxyphenyl)-6-methyl-2-oxo-3,4-dihydro-1H-pyrimidine-5-carboxylate
• CAS: 1026791-46-7
• 化学式: C₁₅H₁₈N₂O₄
• 分子量: 290.319
• InChiKey: ZBBPICFYDJFWNE-ZDUSSCGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  乙酰乙酸乙酯 、 4-甲氧基苯甲醛 、 尿素 在 2,4,6-三氯苯甲酸 、 tert-gutylammonium 2,2,2-trifluoroacetate 、 N-[(1R,2R)-2-aminocyclohexyl]-N'-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-thiourea 作用下， 以 二氯甲烷 为溶剂， 反应 73.0h， 生成 ethyl (4R)-4-(4-methoxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate 、 (S)-(+)-5-ethoxycarbonyl-6-methyl-4-(4-methoxyphenyl)-3,4-dihydropyrimidin-2(1H)-one
  参考文献：
  名称：

  手性双功能伯胺-硫脲催化剂促进的高对映选择性Biginelli反应：二氢嘧啶的不对称合成

  摘要：

  通过Biginelli反应，以中等至高收率（高达99％ee）实现了二氢嘧啶（DHPM）的非对映特异性形成。将反应物通过使用由手性双官能伯胺-硫脲的组合的催化剂进行9F和布朗斯台德酸与叔-butylammonium三氟乙酸盐（叔BuNH 2 ⋅TFA）在室温下在二氯甲烷中的添加剂。已经提出了反应的可能机理来解释活化和不对称诱导的起源。

  DOI：

  10.1002/adsc.200900597

文献信息

• Novel supramolecular organocatalysts of hydroxyprolinamide based on calix[4]arene scaffold for the enantioselective Biginelli reaction
  作者：ZhengYi Li、HuaiJie Xing、GuoLi Huang、XiaoQiang Sun、JuLi Jiang、LeYong Wang

  DOI：10.1007/s11426-011-4374-z

  日期：2011.11

  A series of novel supramolecular organocatalysts of hydroxyprolinamide based on the upper rim of calix[4]arene scaffold have been developed to catalyze enantioselective multi-component Biginelli reaction. Under the optimal conditions, the reactions occurred with moderate-to-excellent enantioselectivities (up to 98% ee). A plausible transition state constructed by the supramolecular interaction of hydrogen bond and cation-π between catalysts and substrates has been proposed.

  一系列基于四甲基源的羟基脯氨酸酰胺新型超分子有机催化剂已经被开发出来，用于催化手性选择性的多组分比吉内利反应。在最佳条件下，反应表现出中等到优异的手性选择性（最高可达98% ee）。提出了一种合理的过渡态，其中催化剂与底物之间的氢键和阳离子-π的超分子相互作用被构建。
• Highly Enantioselective Biginelli Reaction Promoted by Chiral Bifunctional Primary Amine-Thiourea Catalysts: Asymmetric Synthesis of Dihydropyrimidines
  作者：Yangyun Wang、Haitao Yang、Jipan Yu、Zhiwei Miao、Ruyu Chen

  DOI：10.1002/adsc.200900597

  日期：2009.12

  reaction was performed by using a combined catalyst consisting of a chiral bifunctional primary amine-thiourea 9f and a Brønsted acid with tert-butylammonium trifluoroacetate (t-BuNH2⋅TFA) as additive in dichloromethane at room temperature. The possible mechanism for the reaction has been proposed to explain the origin of the activation and the asymmetric induction.

  通过Biginelli反应，以中等至高收率（高达99％ee）实现了二氢嘧啶（DHPM）的非对映特异性形成。将反应物通过使用由手性双官能伯胺-硫脲的组合的催化剂进行9F和布朗斯台德酸与叔-butylammonium三氟乙酸盐（叔BuNH 2 ⋅TFA）在室温下在二氯甲烷中的添加剂。已经提出了反应的可能机理来解释活化和不对称诱导的起源。
• Primary Amine Catalyzed Biginelli Reaction for the Enantioselective Synthesis of 3,4-Dihydropyrimidin-2(1H)-ones
  作者：Derong Ding、Cong-Gui Zhao

  DOI：10.1002/ejoc.201000448

  日期：——

  Several chiral primary amines, mainly those derived from the cinchona alkaloids, were evaluated as the organocatalysts for the asymmetric Biginelli reaction. With the quinine-derived amine catalyst 1 and after extensive optimization of the reaction conditions, 3,4-dihydropyrimidin-2(1H)-ones were obtained in moderate to good yields and 51-78% ee from a three-component reaction of aryl and aliphatic

  几种手性伯胺，主要来自金鸡纳生物碱，被评估为不对称 Biginelli 反应的有机催化剂。使用奎宁衍生的胺催化剂 1 和反应条件的广泛优化后，3,4-二氢嘧啶-2(1H)-酮以中等至良好的收率和 51-78% ee 从芳基的三组分反应中获得和脂肪醛、尿素和乙酰乙酸酯。
• 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。
• 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)。