ethyl (2S)-2-[(4S)-2,2-dimethyl-5-oxo-1,3-dioxan-4-yl]-2-(4-methoxyanilino)acetate | 863921-48-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (2S)-2-[(4S)-2,2-dimethyl-5-oxo-1,3-dioxan-4-yl]-2-(4-methoxyanilino)acetate
• CAS: 863921-48-6
• 化学式: C₁₇H₂₃NO₆
• 分子量: 337.373
• InChiKey: FMQXYQOCEDXUIA-LSDHHAIUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl (2S)-2-[(4S)-2,2-dimethyl-5-oxo-1,3-dioxan-4-yl]-2-(4-methoxyanilino)acetate 在 溶剂黄146 作用下， 以 乙腈 为溶剂， 反应 48.0h， 以90%的产率得到(S)-((4S,5R)-5-Hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl)-(4-methoxy-phenylamino)-acetic acid ethyl ester
  参考文献：
  名称：

  通过不对称有机催化曼尼希反应有效进入氨基糖和衍生物

  摘要：

  通过使用 2,2-二甲基-1,3-二恶烷-5-酮作为磷酸二羟丙酮等价物和 N-PMP 或 N-Boc 的直接不对称有机催化 Mannich 方法，高效仿生 C 3 +C n 进入氨基糖和衍生物已开发出受保护的亚胺。曼尼希碱以高非对映体和对映体过量（78% 至 >99% de，81-98% ee）获得，并使用非对映选择性还原方案以及通过非对映选择性直接还原胺化反应进一步精细化。

  DOI：

  10.1055/s-2006-942542
• 作为产物：
  描述：

  乙醛酸乙酯 、 2,2-二甲基-1,3-二恶烷-5-酮 、 甲氧苯胺 在 水 、 L-脯氨酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 120.0h， 以91%的产率得到ethyl (2S)-2-[(4S)-2,2-dimethyl-5-oxo-1,3-dioxan-4-yl]-2-(4-methoxyanilino)acetate
  参考文献：
  名称：

  通过不对称有机催化曼尼希反应有效进入氨基糖和衍生物

  摘要：

  通过使用 2,2-二甲基-1,3-二恶烷-5-酮作为磷酸二羟丙酮等价物和 N-PMP 或 N-Boc 的直接不对称有机催化 Mannich 方法，高效仿生 C 3 +C n 进入氨基糖和衍生物已开发出受保护的亚胺。曼尼希碱以高非对映体和对映体过量（78% 至 >99% de，81-98% ee）获得，并使用非对映选择性还原方案以及通过非对映选择性直接还原胺化反应进一步精细化。

  DOI：

  10.1055/s-2006-942542

文献信息

• Amino Acid-Catalyzed Asymmetric Carbohydrate Formation: Organocatalytic One-StepDe Novo Synthesis of Keto and Amino Sugars
  作者：Ismail Ibrahem、Weibiao Zou、Yongmei Xu、Armando Córdova

  DOI：10.1002/adsc.200505323

  日期：2006.1

  A direct de novo synthesis of ketoses and amino sugars by amino acid-catalyzed asymmetric aldol, Mannich and Michael reactions with dihydroxyacetone phosphate mimics as donors is presented. Proline, proline derivatives and thiazolidine-4-carboxylic acids catalyzed the asymmetric assembly of keto sugars and amino sugars in high yield with up to >99% ee. The organocatalytic C3+Cn methodology presented

  提出了由氨基酸催化的不对称醛醇，曼尼希和迈克尔反应与二羟基丙酮磷酸酯模拟物作为供体的酮糖和氨基糖的直接从头合成。脯氨酸，脯氨酸衍生物和噻唑烷-4-羧酸以高达99％ee的高收率催化了酮糖和氨基糖的不对称组装。本文介绍的有机催化C 3 + C n方法是直接合成正交保护的C 4，C 5和C 6的从头合成酮糖，碳水化合物衍生物，氨基和氮杂糖以及聚草酰胺酸的总合成。添加水显着促进并改善了脯氨酸介导的仿生不对称CC键形成反应的对映选择性。
• Acyclic Chiral Amines and Amino Acids as Inexpensive and Readily Tunable Catalysts for the Direct Asymmetric Three-Component Mannich Reaction
  作者：Ismail Ibrahem、Weibiao Zou、Magnus Engqvist、Yongmei Xu、Armando Córdova

  DOI：10.1002/chem.200500746

  日期：2005.11.18

  The direct three-component asymmetric Mannich reaction catalyzed by acyclic chiral amines or amino acids is presented. Simple acyclic chiral amines and amino acids--such as alanine-tetrazole (9), alanine, valine, and serine-catalyzed the three-component asymmetric Mannich reactions between unmodified ketones, p-anisidine, and aldehydes with high chemo- and stereoselectivity, furnishing the corresponding

  提出了由无环手性胺或氨基酸催化的直接三组分不对称曼尼希反应。简单的无环手性胺和氨基酸-丙氨酸-四唑（9），丙氨酸，缬氨酸和丝氨酸可催化未修饰的酮，对茴香脑和醛之间的三组分不对称曼尼希反应，具有高的化学和立体选择性，为相应的曼尼希基地提供高达99％的ee。这项研究表明，可以在设计和优化用于直接不对称曼尼希反应的新型廉价有机催化剂中考虑自然界中所有氨基酸以及非蛋白氨基酸衍生物。
• Organocatalytic Synthesis and Anti‐Trypanosomal Activity Evaluation of L‐Pentofuranose‐Mimetic Iminosugars
  作者：Juan M. Mesa、Marcelo A. Comini、Estefanía Dibello、Daniela Gamenara

  DOI：10.1002/ejoc.202200636

  日期：2022.9.13

  reaction of an imine and a protected dioxanone is described as the key step for the stereoselective synthesis of a series of L-lyxo and L-xylo- pentofuranose-mimetic iminosugars and derivatives. The L-lyxo derivative 12, has emerged as head of series, seeking for the development of novel glycomimetics with potential activity towards pathogenic trypanosomatids.

  D-脯氨酸催化的亚胺和受保护的二恶烷酮的曼尼希反应被描述为立体选择性合成一系列 L - lyxo和 L-木糖-呋喃戊糖模拟亚氨基糖及其衍生物的关键步骤。L -lyxo衍生物12已成为系列的负责人，寻求开发对致病性锥虫具有潜在活性的新型糖模拟物。
• Dihydroxyacetone in Amino Acid Catalyzed Mannich-Type Reactions
  作者：Bernhard Westermann、Christiane Neuhaus

  DOI：10.1002/anie.200500297

  日期：2005.6.27
• Microwave-Assisted Asymmetric Organocatalysis. A Probe for Nonthermal Microwave Effects and the Concept of Simultaneous Cooling
  作者：Masood Hosseini、Nikola Stiasni、Vera Barbieri、C. Oliver Kappe

  DOI：10.1021/jo0624187

  日期：2007.2.1

  [GRAPHICS]A series of five known asymmetric organocatalytic reactions was re-evaluated at elevated temperatures applying both microwave dielectric heating and conventional thermal heating in order to probe the existence of specific or nonthermal microwave effects. All transformations were conducted in a dedicated reactor setup that allowed accurate internal reaction temperature measurements using fiber-optic probes. In addition, the concept of simultaneous external cooling while irradiating with microwave power was also applied in all of the studied cases. This method allows a higher level of microwave power to be administered to the reaction mixture and, therefore, enhances any potential microwave effects while continuously removing heat. For all of the five studied (S)-proline-catalyzed asymmetric Mannich- and aldol-type reactions, the observed rate enhancements were a consequence of the increased temperatures attained by microwave dielectric heating and were not related to the presence of the microwave field. In all cases, in contrast to previous literature reports, the results obtained either with microwave irradiation or with microwave irradiation with simultaneous cooling could be reproduced by conventional heating at the same reaction temperature and time in an oil bath. No evidence for specific or nonthermal microwave effects was obtained.