ethyl (R)-6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate

• 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: ethyl (R)-6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate
• 英文别名: (R)-(-)-5-ethoxycarbonyl-6-methyl-4-phenyl-3,4-dihydropyrimidin-2(1H)-one；ethyl 6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate；(R)-5-ethoxycarbonyl-6-methyl-4-phenyl-3,4-dihydropyrimidin-2(1H)-one；5-ethoxycarbonyl-6-methyl-4-phenyl-3,4-dihydropyrimidin-2(1H)-one；ethyl (4R)-6-methyl-2-oxo-4-phenyl-3,4-dihydro-1H-pyrimidine-5-carboxylate
• 化学式: C₁₄H₁₆N₂O₃
• mdl: MFCD00124778
• 分子量: 260.293
• InChiKey: URMNHHAUVFEMIG-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  19
• 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：

  6-甲基-2-氧代-4-苯基-1,2,3,4-四氢-5-嘧啶羧酸乙酯 生成 ethyl (R)-6-methyl-2-oxo-4-phenyl-1,2,3,4-tetrahydropyrimidine-5-carboxylate
  参考文献：
  名称：

  Separation of enantiomers of 4-aryldihydropyrimidines by direct enantioselective HPLC. A critical comparison of chiral stationary phases

  摘要：

  The separation of the enantiomers of 29 racemic 4-aryldihydropyrimidine-5-carboxylates (DHPMs), aza-analogs of nifedipine-type dihydropyridine calcium channel modulators, was evaluated in direct enantioselective HPLC, employing the following commercially available chiral stationary phases (CSPs): Chiralcel OD-H, ChiraDex, Chirobiotic V and T, and Whelk-O1. In addition, a 1,2-diphenyl-1,2-diaminoethane based CSP and two quinine carbamate based chiral ion exchangers were also employed. For all 29 DHPMs separation of individual enantiomers could be achieved with at least one CSP with alpha-values ranging from 1.10 to 8.67. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00214-0

文献信息

• An Enantioselective Biginelli Reaction Catalyzed by a Simple Chiral Secondary Amine and Achiral Brønsted Acid by a Dual-Activation Route
  作者：Junguo Xin、Lu Chang、Zongrui Hou、Deju Shang、Xiaohua Liu、Xiaoming Feng

  DOI：10.1002/chem.200701581

  日期：2008.3.27

  An enantioselective Biginelli reaction that proceeds by a dual-activation route has been developed by using a combined catalyst of a readily available trans-4-hydroxyproline-derived secondary amine and a Bronsted acid. Aromatic, heteroaromatic, and fused-ring aldehydes were found to be suitable substrates for this multicomponent reaction. The corresponding dihydropyrimidines were obtained in moderate-to-good

  通过使用容易获得的反式4-羟基脯氨酸衍生的仲胺和布朗斯台德酸的组合催化剂，已经开发了通过双活化途径进行的对映选择性比吉内利反应。发现芳族，杂芳族和稠环醛是该多组分反应的合适底物。在温和条件下，以中等至良好的收率获得了相应的二氢嘧啶，收率高达98％ee。根据实验结果和观察到的产物的绝对构型，提出了一个合理的过渡态来解释激活和不对称诱导的起源。
• Highly enantioselective Biginelli reaction catalyzed by a simple chiral primary amine catalyst: asymmetric synthesis of dihydropyrimidines
  作者：Da-Zhen Xu、Hui Li、Yongmei Wang

  DOI：10.1016/j.tet.2012.07.027

  日期：2012.9

  Several chiral primary amines were introduced as organocatalysts for the asymmetric Biginelli reaction. The reaction was performed by using a combined catalyst consisting of a chiral bifunctional primary amine–pyridine 5j and hydrochloric acid in a mixed solvent of 1,4-dioxane/CHCl3 (8/2, v/v) at room temperature. The corresponding dihydropyrimidines were obtained in moderate to high yields with up

  几种手性伯胺被引入作为不对称Biginelli反应的有机催化剂。反应是在室温下，使用由手性双官能伯胺-吡啶5j和盐酸组成的混合催化剂在1,4-二恶烷/ CHCl 3（8/2，v / v）的混合溶剂中进行的。在温和条件下，以中等至高收率获得了相应的二氢嘧啶，其中ee高达> 99％。
• NOVEL PICOLINAMIDE-CINCHONA ORGANOCATALYSTS AND DERIVATIVES
  申请人：UNIVERSIDADE DE ÉVORA

  公开号：US20160236184A1

  公开（公告）日：2016-08-18

  The present application describes a novel type of picolinamide-cinchona organocatalyst that allows for the successful transformation of ketimines to chiral amines with very high enantioselectivities and with the highest TOFs reported for any particular organocatalyst to date. These organocatalysts have also been immobilized to a variety of solid supports, including magneto-nanoparticles.

  本申请描述了一种新型的吡啶甲酰喹诺酮有机催化剂，可以成功地将酮亚胺转化为手性胺，具有非常高的对映选择性，并且具有迄今为止报道的任何特定有机催化剂中最高的TOFs。这些有机催化剂还被固定在各种固体支撑物上，包括磁性纳米颗粒。
• 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。
• Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis
  作者：Marcus Frings、Isabelle Thomé、Carsten Bolm

  DOI：10.3762/bjoc.8.164

  日期：——

  For the first time, chiral sulfoximine derivatives have been applied as asymmetric organocatalysts. In combination with a thiourea-type backbone the sulfonimidoyl moiety leads to organocatalysts showing good reactivity in the catalytic desymmetrization of a cyclic meso-anhydride and moderate enantioselectivity in the catalytic asymmetric Biginelli reaction. Straightforward synthetic routes provide the newly designed thiourea-sulfoximine catalysts in high overall yields without affecting the stereohomogeneity of the sulfur-containing core fragment.

  首次，手性亚磺酰胺衍生物被应用为不对称有机催化剂。与硫脲型骨架结合，磺酰亚胺基团导致催化剂在对称催化环状meso-酸酐的去对称化反应中表现出良好的反应性，并在催化不对称Biginelli反应中显示出中等的对映选择性。直接合成路线以高总产率提供新设计的硫脲-亚磺酰胺催化剂，而不影响含硫核心片段的立体同质性。