(R)-4-((R)-hydroxy(4-nitrophenyl)methyl)-2,2-dimethyl-1,3-dioxan-5-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: (R)-4-((R)-hydroxy(4-nitrophenyl)methyl)-2,2-dimethyl-1,3-dioxan-5-one
• 英文别名: (4R)-4-[(R)-hydroxy-(4-nitrophenyl)methyl]-2,2-dimethyl-1,3-dioxan-5-one
• 化学式: C₁₃H₁₅NO₆
• 分子量: 281.265
• InChiKey: FGFGLSBDAMHTEX-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2,2-二甲基-1,3-二恶烷-5-酮 、 对硝基苯甲醛 在 (1S,3R,4S)-3-amino-4-(trifluoromethanesulfonylamino)cyclohexanecarboxylic acid ethyl ester 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 (R)-4-((R)-hydroxy(4-nitrophenyl)methyl)-2,2-dimethyl-1,3-dioxan-5-one 、 4-(hydroxy(4-nitrophenyl)methyl)-2,2-dimethyl-1,3-dioxan-5-one
  参考文献：
  名称：

  使用来自共同手性来源的两种不同手性有机催化剂在不对称直接醛醇反应中完全转换产物选择性

  摘要：

  通过从易于获得的受保护顺式二胺化合物作为常见手性来源设计两种不同的手性有机催化剂，开发了一种用于不对称合成两种对映异构醛醇产物的新方法。从实用的角度来看，这种方法非常有用。

  DOI：

  10.1021/ja807807p

文献信息

• Asymmetric Aldol Reaction Catalyzed by a Heterogenized Proline on a Mesoporous Support. The Role of the Nature of Solvents
  作者：Elisa G. Doyagüez、Félix Calderón、Félix Sánchez、Alfonso Fernández-Mayoralas

  DOI：10.1021/jo070992s

  日期：2007.11.1

  heterogenized (S)-proline on mesoporous support MCM-41 catalyzes the asymmetric aldol reaction in a wide range of solvents. The progress of the reaction is dependent on the nature of the solvent. Reactions proceed more efficiently in hydrophilic polar solvents; however, the addition of a small amount of water has a positive effect on the rate and the stereoselectivity of the reaction performed in hydrophobic

  介孔载体MCM-41上的杂化（S）-脯氨酸可在多种溶剂中催化不对称的羟醛反应。反应的进行取决于溶剂的性质。在亲水性极性溶剂中，反应可以更有效地进行；然而，添加少量的水对在疏水性甲苯中进行的反应的速率和立体选择性具有积极的影响。在非均相条件下的反应也已经在手性醛上进行，提供了用于合成氮杂糖的有用中间体。
• Highly Stereoselective and Scalable <i>anti</i>-Aldol Reactions Using <i>N</i>-(<i>p</i>-Dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide: Scope and Origins of Stereoselectivities
  作者：Hua Yang、Subham Mahapatra、Paul Ha-Yeon Cheong、Rich G. Carter

  DOI：10.1021/jo1015008

  日期：2010.11.5

  A highly enantio- and diastereoselective anti-aldol process (up to >99% ee, >99:1 dr) catalyzed by a proline mimetic—N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide—has been developed. Catalyst loading as low as 2 mol % can be employed. Use of industry-friendly solvents for this transformation as well as neat reaction conditions have been demonstrated. The scope of this transformation on a range

  一种由脯氨酸模拟物N- (对十二烷基苯磺酰基)-2-吡咯烷甲酰胺催化的高度对映和非对映选择性反羟醛过程（高达 >99% ee，>99:1 dr）已被开发出来。可以使用低至2mol%的催化剂负载。已经证明可以使用工业友好型溶剂进行这种转化以及纯净的反应条件。探索了这种对一系列醛和酮的转化范围。密度泛函理论计算表明，增强的非对映选择性的起源是由于磺酰胺、亲电子试剂和催化剂烯胺之间存在非经典氢键，有利于 Houk−List 模型中主要的反 Re 醛醇TS 。
• 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。
• New small γ-turn type <i>N</i>-primary amino terminal tripeptide organocatalyst for solvent-free asymmetric aldol reaction of various ketones with aldehydes
  作者：Rajkumar Thiyagarajan、Zubeda Begum、Chigusa Seki、Yuko Okuyama、Eunsang Kwon、Koji Uwai、Michio Tokiwa、Suguru Tokiwa、Mitsuhiro Takeshita、Hiroto Nakano

  DOI：10.1039/d1ra08635a

  日期：——

  New small γ-turn type N-primary amino terminal tripeptides were synthesized and their functionality as an organocatalyst was examined in the asymmetric aldol reaction of various ketones with different aromatic aldehydes under solvent-free neat conditions to afford the desired chiral anti-aldol products in good to excellent chemical yields, diastereoselectivities and enantioselectivities (up to 99%

  合成了新的小γ-转角型N-伯氨基末端三肽，并在无溶剂纯净条件下各种酮与不同芳香醛的不对称羟醛反应中检查了它们作为有机催化剂的功能，以提供所需的手性反羟醛产物良好至优异的化学收率、非对映选择性和对映选择性（高达 99%，高达 syn : anti/13 : 87 dr，高达 99% ee）。
• Dihydroxyacetone Variants in the Organocatalytic Construction of Carbohydrates:  Mimicking Tagatose and Fuculose Aldolases
  作者：Jeff T. Suri、Susumu Mitsumori、Klaus Albertshofer、Fujie Tanaka、Carlos F. Barbas

  DOI：10.1021/jo0602017

  日期：2006.5.1

  Dihydroxyacetone variants have been explored as donors in organocatalytic aldol reactions with various aldehyde and ketone acceptors. The protected form of dihydroxyacetone that was chosen for in-depth study was 2,2-dimethyl-1,3-dioxan-5-one, 1. Among the catalysts surveyed here, proline proved to be superior in terms of yield and stereoselectivities in the construction of various carbohydrate scaffolds. In a fashion analogous to aldolase enzymes, the de novo preparation of L-ribulose, L-lyxose, D-ribose, D-tagatose, 1-amino-1-deoxy-D-lyxitol, and other carbohydrates was accomplished via the use of 1 and proline. In reactions using 2,2-dimethyl-1,3-dioxan-5-one 1 as a donor, (S)-proline can be used as a functional mimic of tagatose aldolase, whereas (R)-proline can be regarded as an organocatalytic mimic of fuculose aldolase.