(3R,4R)-3-hydroxy-4-(4-methoxyphenylamino)-4-(4-nitrophenyl)butan-2-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3R,4R)-3-hydroxy-4-(4-methoxyphenylamino)-4-(4-nitrophenyl)butan-2-one
• 英文别名: (3R,4R)-3-hydroxy-4-(p-methoxyphenylamino)-4-(p-nitrophenyl)butan-2-one；(3R,4R)-3-hydroxy-4-(p-methoxyphenyamino)-4-(p-nitrophenyl)butan-2-one；3-hydroxy-4-(p-methoxyphenyamino)-4-(p-nitrophenyl)butan-2-one；(3R,4R)-3-hydroxy-4-(4-methoxyanilino)-4-(4-nitrophenyl)butan-2-one
• 化学式: C₁₇H₁₈N₂O₅
• 分子量: 330.34
• InChiKey: MVQRRRLRTOWWPU-SJORKVTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  104
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  (E)-4-methoxy-N-(4-nitrobenzylidene)aniline 、 羟基丙酮 在 O-t-Bu-L-threonine 作用下， 以 二甲基亚砜 为溶剂， 反应 22.0h， 生成 (3R,4R)-3-hydroxy-4-(4-methoxyphenylamino)-4-(4-nitrophenyl)butan-2-one 、 (3S,4S)-3-hydroxy-4-(4-methoxyphenylamino)-4-(4-nitrophenyl)butan-2-one
  参考文献：
  名称：

  通过有机催化反曼尼希和合成羟醛反应直接催化不对称合成反 1,2-氨基醇和syn-1,2-二醇

  摘要：

  手性 1,2-氨基醇和 1,2-二醇是在大量天然和生物活性分子中发现的常见结构基序。已经报道了使用基于金属的策略有效对映选择性合成含有顺-或反-1,2-氨基醇和1,2-二醇的酮。然而，迄今为止，涉及有机催化的方法仅限于合成 1,2-氨基醇和反 1,2-二醇。在此，我们公开了通过直接不对称曼尼希、曼尼希型和羟醛反应（涉及未修饰的 α-羟基酮在伯胺催化的反应中）制备高度对映体富集的抗 1,2-氨基醇和合成 1,2-二醇的简单有效途径-含氨基酸。这些反应利用处于成键过渡态的 α-羟基酮的 (Z)-烯胺。这项研究补充并扩展了我们在这两种多功能合成子类中进行不对称合成的生物有机方法。值得注意的是，这些反应是实用的，耐受湿溶剂，并且...

  DOI：

  10.1021/ja0677012

文献信息

• Isosteviol-amino Acid Conjugates as Highly Efficient Organocatalysts for the Asymmetric One-pot Three-component Mannich Reactions
  作者：Yajie An、Qian Qin、Chuanchuan Wang、Jingchao Tao

  DOI：10.1002/cjoc.201180272

  日期：2011.7

  Isosteviol‐amino acid conjugates were synthesized and used as chiral catalysts for the asymmetric three‐component Mannich reaction with hydroxyacetone as donor molecule. Good yields (up to 98%) and excellent stereoselectivities (up to 97:3 dr and 99% ee) were achieved in a short reaction time. In addition, syn‐ or anti‐configurations of α‐hydroxy‐β‐amino carbonyl compounds were obtained as main products

  合成了异戊烯醇-氨基酸共轭物，并用作手性催化剂，用于以羟丙酮为供体分子的不对称三组分曼尼希反应。在较短的反应时间内即可获得良好的收率（高达98％）和出色的立体选择性（高达97：3 dr和99％ee）。此外，S炔-或反的-configurations α羟基β -氨基得到羰基化合物作为主要产品具有不同的手性催化剂。
• Threonine-surfactant organocatalysts for the highly diastereo- and enantioselective direct anti-Mannich reactions of hydroxyacetone
  作者：Chuanlong Wu、Xiangkai Fu、Xuebing Ma、Shi Li、Chao Li

  DOI：10.1016/j.tetlet.2010.08.085

  日期：2010.11

  by the reaction of threonine with acyl chlorides at room temperature in trifluoroacetic acid on a large-scale without protecting groups involved or chromatographic techniques, and those threonine-surfactant organocatalysts mediated the direct asymmetric anti-Mannich reactions of hydroxyacetone and anilines with aldehydes to synthesize anti-1,2-amino alcohols in good yields (75–93%) and highly enantioselectivities

  在这项工作中，第一步是在室温下将苏氨酸与酰氯在三氟乙酸中大规模反应而没有涉及的保护基团或色谱技术，一次合成了几种新的作为有机催化剂的l-苏氨酸衍生物。苏氨酸表面活性剂有机催化剂介导了羟基丙酮和苯胺与醛的直接不对称抗曼尼希反应，以高收率（75-93％）和高对映选择性（高达99％ee）合成抗-1,2-氨基醇。
• Highly efficient chiral polydentate sulfinyl ligands/catalysts containing prolinol moiety
  作者：Jacek Chrzanowski、Michał Rachwalski、Adam M. Pieczonka、Stanisław Leśniak、Józef Drabowicz、Piotr Kiełbasiński

  DOI：10.1016/j.tet.2015.05.103

  日期：2016.5

  New polydentate chiral ligands, containing the hydroxyl group, stereogenic sulfinyl group and enantiomeric prolinol moieties were synthesized and proved very efficient catalysts in the asymmetric diethylzinc addition to benzaldehyde, the asymmetric aldol condensation and the asymmetric Mannich reaction. Replacement of the central hydroxyl group with the second prolinol moiety of the same absolute configuration gave new ligands in which the sulfinyl group was not a stereogenic centre anymore, but which proved almost equally efficient as catalysts for the reactions investigated. The absolute configuration of the proline moiety exerted a decisive impact on the stereochemical outcome of these reactions, deciding about the absolute configuration of the products formed. (C) 2015 Elsevier Ltd. All rights reserved.
• Continuous Flow Enantioselective Three-Component <i>anti</i>-Mannich Reactions Catalyzed by a Polymer-Supported Threonine Derivative
  作者：Carles Ayats、Andrea H. Henseler、Estefanía Dibello、Miquel A. Pericàs

  DOI：10.1021/cs5006037

  日期：2014.9.5

  A series of primary amino acid-derived polystyrene-supported organocatalysts was tested in antiselective Mannidi reactions. The polystyrene-immobilized threonine derivative showed the best performance in threecomponent (hydroxyacetone, anilines, and aldehydes) Mannich reactions to provide anti-beta-amino-alpha-hydroxycarbonyl compounds (11 examples; up to 95% ee), and its use could be extended to dihydroxyacetone and protected hydroxyace-tones (7 examples; up to 90% ee). The high activity depicted by the catalyst has allowed its implementation in continuous flow. Under this operation mode, the supported threonine catalyst produces anti-Mannich adducts with generally higher diastereo- and enantioselectivity than in batch. A family of five different enantioenriched anti-Mannich adducts has been sequentially prepared in flow by passing different combinations of anilines and aromatic aldehydes over the same sample of catalyst. This confirms the suitability of this methodology for the rapid access to small libraries of enantioenriched compounds.
• Enantioselective Organocatalytic Mannich Reactions with Autocatalysts and Their Mimics
  作者：Xinbo Wang、Yongbo Zhang、Haibo Tan、Yanchao Wang、Peng Han、David Zhigang Wang

  DOI：10.1021/jo902500b

  日期：2010.4.2

  The Mannich reactions previously extensively investigated with organocatalysis of L-proline and other related small molecules were reinvestigated with detailed stercochemical analysis of their autocatalysis pathways, through employment of both the products themselves and their close structural mimics as the catalysts. These organo-autocatalytic processes function as meaningful molecular models toward understanding the origin and maintenance of homochirality under biologically relevant conditions.