(3R,4S)-3,4-dihydroxy-4-(2-nitrophenyl)butan-2-one | 956403-65-9

• 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,4S)-3,4-dihydroxy-4-(2-nitrophenyl)butan-2-one
• CAS: 956403-65-9
• 化学式: C₁₀H₁₁NO₅
• 分子量: 225.201
• InChiKey: XAPHDBGLNQPKIJ-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  103
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3R,4S)-3,4-dihydroxy-4-(2-nitrophenyl)butan-2-one 在 sodium tetrahydroborate 、 水 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以80%的产率得到(1S,2R,3R)-1-(2-nitrophenyl)butane-1,2,3-triol
  参考文献：
  名称：

  (S)-Threonine/α,α-(S)-diphenylvalinol-derived chiral ionic liquid: an immobilized organocatalyst for asymmetric syn-aldol reactions

  摘要：

  Chiral ionic liquids containing (S)- or (R)-threonine amide and alpha,alpha-(S)-diphenylvalinol units were synthesized In the presence of the (S)-threonine-derived catalyst reactions between ketones with secondary carbon atom(s) at the alpha-position with respect to the carbonyl group and aromatic (heteroaromatic) aldehydes afforded the corresponding syn-aldols in high yields (up to 99%) and with high diastereo-(syn/anti up to 97:3) and enantioselectivity (up to 99% ee), which was maintained over three reaction cycles. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.01.017
• 作为产物：
  描述：

  羟基丙酮 、 邻硝基苯甲醛 在 1-(4-{(2S)-2-amino-2-[(S)-1-(hydroxy-diphenyl-methyl)-2-methyl-propylcarbamoyl]-(R)-1-methyl-ethoxycarbonyl}-butyl)-3-methyl-3H-imidazol-1-ium hexafluorophosphates 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以94%的产率得到(3R,4S)-3,4-dihydroxy-4-(2-nitrophenyl)butan-2-one
  参考文献：
  名称：

  用于不对称合成羟醛反应的可持续氨基酸衍生有机催化剂

  摘要：

  鉴定了在不对称醛醇反应中导致伯氨基酸衍生的有机催化剂快速失活的不良副过程。基于这些结果设计了一种新的离子液体负载的 (S)-缬氨酸-/(S)-α,α-二苯基丝氨醇衍生催化剂 (9) 并在羟基丙酮之间的不对称合成羟醛反应中表现出更好的可回收性和醛类。此外，该催化剂似乎可用于通过不对称合成羟醛/内酯化级联反应立体选择性合成天然存在的 1(3H)-isobenzofuran-1-one 支架。

  DOI：

  10.1002/ejoc.201700166

文献信息

• Chiral Primary−Tertiary Diamine Catalysts Derived From Natural Amino Acids for <i>syn</i>-Aldol Reactions of Hydroxy Ketones
  作者：Jiuyuan Li、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1021/jo802557p

  日期：2009.2.20

  A series of primary-tertiary diamine catalysts were designed and synthesized from primary natural amino acids. Application of these new chiral catalysts in direct aldol reactions of α-hydroxyketones showed very good catalytic activity (up to 97% yield) and high syn selectivity (up to syn/ anti = 30:1, 99% ee).

  从伯天然氨基酸设计合成了一系列伯叔二胺催化剂。这些新的手性催化剂在α-羟基酮的直接醛醇缩合反应中的应用显示出非常好的催化活性（高达97％的收率）和高的合成选择性（高达syn / anti = 30：1，99％ee）。
• A Highly Efficient, Large-Scale, Asymmetric Direct Aldol Reaction Employing Simple Threonine Derivatives as Recoverable Organocatalysts in the Presence of Water
  作者：Chuanlong Wu、Xiangkai Fu、Shi Li

  DOI：10.1002/ejoc.201001396

  日期：2011.3

  A one-step O-acylation of threonine resulted in a simple and readily available threonine-surfactant organocatalyst that could efficiently catalyze the direct asymmetric aldol reactions of cyclic and acyclic ketones with a series of aromatic aldehydes in the presence of water at room temperature with good yields (up to 99 %), diastereoselectivities (up to 99:1), and enantiomeric excesses (>99 %). The

  苏氨酸的一步 O-酰化产生了一种简单易得的苏氨酸 - 表面活性剂有机催化剂，它可以在室温下在水的存在下有效地催化环状和非环状酮与一系列芳香醛的直接不对称醛醇反应。产率（高达 99%）、非对映选择性（高达 99:1）和对映体过量（>99%）。该催化剂可以很容易地回收和重复使用，六次循环后对映选择性不会降低。这种新型催化剂可以有效地用于大规模反应，同时对映选择性保持在同一水平，为工业应用提供了很大的可能性。
• Highly efficient direct a larger-scale aldol reactions catalyzed by a flexible prolinamide based-metal Lewis acid bifunctional catalyst in the presence of water
  作者：Guodong Chen、Xiangkai Fu、Chao Li、Chuanlong Wu、Qiang Miao

  DOI：10.1016/j.jorganchem.2011.12.006

  日期：2012.4

  prolinamide-based organocatalysts were readily synthesized and applied to the asymmetric direct aldol reactions of ketones and aromatic aldehydes in the presence of water. When TFA was used as an acidic additive, 10 mol % loading of 1c afforded aldol products with good diastereoselectivity of up to 91/9 and enantioselectivity of up to 85%. When ZnCl2 was added as a metal Lewis acid additive, the aldol product

  在这项工作中，很容易合成四种基于脯氨酰胺的有机催化剂，并将其应用于在水存在下酮和芳族醛的不对称直接羟醛反应。当TFA用作酸性添加剂，的10％摩尔负载量1c中，得到羟醛产品具有多达的非对映选择性良好至91/9和高达85％的对映选择性。当添加ZnCl 2作为金属路易斯酸添加剂时，可获得高达99/1 dr和96％ee的羟醛产物。这种新型的基于脯氨酰胺的金属路易斯酸双功能有机催化剂1c 可以将对映选择性保持在相同水平有效地用于大规模反应，这为工业应用提供了很大的可能性。
• Pepsin-catalyzed direct asymmetric aldol reactions for the synthesis of vicinal diol compounds
  作者：Ling-Yu Li、Da-Cheng Yang、Zhi Guan、Yan-Hong He

  DOI：10.1016/j.tet.2015.01.061

  日期：2015.3

  The catalytic promiscuity of pepsin from porcine gastric mucous was observed in catalysis of the direct asymmetric aldol reactions of aromatic aldehydes with acetones, which were substituted by hydroxy-, dihydroxy-, methoxy- and benzyloxy- for the synthesis of diol compounds in acetonitrile. This biocatalysis was also applicable to the aldol reactions of cyclic or hetereocyclic ketones with aromatic

  在催化芳香族醛与丙酮直接不对称醛醇缩合反应的催化过程中，观察到了胃蛋白酶对胃蛋白酶的混杂作用，丙酮醛被羟基，二羟基，甲氧基和苄氧基所取代，从而在乙腈中合成二醇化合物。该生物催化也适用于环状或杂环酮与芳族醛的醛醇缩合反应。获得了高达87％的产率，高达> 99/1 dr的非对映选择性和高达75％ee的对映选择性。
• A phosphotungstic acid-supported multifunctional organocatalyst containing 9-amino(9-deoxy)epi-cinchonidine and Brønsted acid and its application in asymmetric aldol reaction
  作者：Ling Lan、Guangxin Xie、Tao Wu、Dandan Feng、Xuebing Ma

  DOI：10.1039/c6ra08909g

  日期：——

  or p-substituted benzaldehydes bearing electron-withdrawing substituents (–X and –NO2) afforded good yields (71–96%) and excellent stereoselectivities (anti/syn = 94/6–98/2, 87–97% ee). It was found that the arm length (n) and acid capacity had significant effects on the cooperative catalysis of CDNH2 and Brøsted acid in the aldol reaction. After the completion of the aldol reaction, the catalysts could

  通过将钨酸钠与有机膦酸一起快速沉淀，开发了一种新型的负载型多功能有机催化剂CDNH 2（n）-HPW ，在磷钨酸的骨架中结合了9-氨基（9-脱氧）表-新可可宁（CDNH 2）和布朗斯台德酸。。向带有吸电子取代基（–X和–NO 2）的o，m或p取代的苯甲醛中环己酮的醛醇加成可提供良好的收率（71–96％）和出色的立体选择性（anti / syn = 94 / 6–98 / 2，87–97％ee）。发现臂长（n）和酸容量对醛醇缩合反应中CDNH 2和Brøsted酸的协同催化有重要影响。醛醇缩合反应完成后，通过离心可以容易地以定量收率回收催化剂，并且具有良好的可重复使用性，并且在五个连续的不对称醛醇缩合反应中没有明显的催化性能损失。