2-硝基-5-氧代己酸甲酯 | 83483-17-4

• 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
• 中文名称: 2-硝基-5-氧代己酸甲酯
• 英文名称: methyl 2-nitro-5-oxohexanoate
• CAS: 83483-17-4
• 化学式: C₇H₁₁NO₅
• 分子量: 189.168
• InChiKey: UEGDXIKRFJPLBN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  89.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-硝基-5-氧代己酸甲酯 在 二甲基硫 、 sodium methylate 、 臭氧 作用下， 以 溶剂黄146 为溶剂， 反应 18.17h， 生成 3-<2-(Methoxycarbonyl)-5-methyl-1-pyrrolyl>propanoic Acid
  参考文献：
  名称：

  Preparation of methyl 2,5-dioxohexanoate: a highly convenient reagent for the introduction of the 2-carbalkoxy-1,5-dialkylpyrrole nucleus

  摘要：

  DOI：

  10.1021/jo00164a028
• 作为产物：
  描述：

  硝基乙酸甲酯 、 丁烯酮 在 18-冠醚-6 、 C₈₀H₄₈N₈Pd₂⁽⁴⁺⁾*4C₃₂H₁₂BF₂₄^(1-) 作用下， 以 二氯甲烷-D2 为溶剂， 反应 0.7h， 以98%的产率得到2-硝基-5-氧代己酸甲酯
  参考文献：
  名称：

  协同非共价催化促进无碱迈克尔加成

  摘要：

  涉及使用强布朗斯台德碱对弱酸性 CH 亲核试剂进行去质子化的碳-碳键形成过程是合成方法的核心。酶也催化弱 CH 酸性底物形成 CC 键，然而，它们在 pH 7 时仅使用非共价相互作用的集合来实现这一点。在这里，我们展示了一个简单的、受生物启发的合成笼催化迈克尔加成反应，仅使用库仑和其他弱相互作用来激活各种亲核试剂和亲电试剂。笼子的阴离子稳定特性促进了自发的亲核试剂去质子化，表明酸度增强相当于几个 pKa 单位。使用第二种非共价试剂 - 市售的 18-crown-6 - 促进了几个具有挑战性的迈克尔伙伴的催化无碱添加。

  DOI：

  10.1021/jacs.0c08639

文献信息

• Highly Efficient Ytterbium Triflate Catalyzed Michael Additions of α-Nitroesters in Water
  作者：Erik Keller、Ben Feringa

  DOI：10.1055/s-1997-5761

  日期：1997.7

  Michael additions of alpha-nitroesters with enones and alpha,beta-unsaturated aldehydes result in quantitative conversions to the corresponding 1,4-adducts by performing the reactions in water in the presence of ytterbium triflate as water-tolerant Lewis acid.

  通过在三氟甲磺酸镱作为耐水路易斯酸的存在下在水中进行反应，α-硝基酯与烯酮和 α，β-不饱和醛的迈克尔加成导致定量转化为相应的 1,4-加合物。
• Enantioselective Synthesis of Quaternary α-Amino Acids Enabled by the Versatility of the Phenylselenonyl Group
  作者：Antonin Clemenceau、Qian Wang、Jieping Zhu

  DOI：10.1002/chem.201604781

  日期：2016.12.19

  conjugate addition of α‐alkyl substituted α‐nitroacetates to phenyl vinyl selenone was developed. The resulting enantio‐enriched α,α‐dialkyl substituted α‐nitroacetates were subsequently converted to various cyclic and acyclic quaternary α‐amino acids, taking advantage of the rich functionalities of the resulting Michael adducts. Novel protocols allowing chemoselective reduction of phenyl selenone to

  开发了一种新的金鸡纳生物碱催化的α-烷基取代的α-硝基乙酸酯向苯乙烯基硒酮的对映选择性共轭加成物。然后利用生成的迈克尔加合物的丰富功能，将生成的对映体富集的α，α-二烷基取代的α-硝基乙酸盐转化为各种环状和无环的季α-氨基酸。还报道了新颖的方案，其允许将苯硒酮化学选择性地还原成苯基硒化物并将烷基苯基硒酮还原成烷烃。
• A NEW METHOD FOR REGIOSELECTIVE α-MONO- OR α,α-DI-DEUTERATION OF CARBONYL COMPOUNDS
  作者：Noboru Ono、Isami Hamamoto、Hideyoshi Miyake、Aritsune Kaji

  DOI：10.1246/cl.1982.1079

  日期：1982.7.5

  Mono- or di-deuterated carbonyl compounds are prepared regioselectively by the base-catalyzed H–D exchange of α-hydrogen of aliphatic nitro compounds and the subsequent replacement of the nitro group by H or D with Bu3SnX (X = H, D).

  通过碱催化脂肪族硝基化合物的 α-氢的 H-D 交换以及随后用 Bu3SnX (X = H, D) 用 H 或 D 取代硝基基团，区域选择性地制备单或二氘代羰基化合物。
• Bifunctional Squaramide Catalysts with the Same Absolute Chirality for the Diastereodivergent Access to Densely Functionalised Cyclohexanes through Enantioselective Domino Reactions. Synthesis and Mechanistic Studies
  作者：Jose I. Martínez、Laura Villar、Uxue Uria、Luisa Carrillo、Efraím Reyes、Jose L. Vicario

  DOI：10.1002/adsc.201400502

  日期：2014.11.24

  AbstractWe have developed a procedure for the stereoselective and diastereodivergent synthesis of densely functionalised cyclohexanes containing four stereocentres through an asymmetric Michael‐initiated ring closure (MIRC) cascade reaction employing hydrogen‐bond catalysis, which is able to prepare adducts with different absolute configurations starting from the same starting materials. The overall process involves a highly diastereo‐ and enantioselective Michael/Henry cascade reaction between a wide range of nitroalkenes and α‐nitro‐δ‐oxo esters, allowing access to different diastereoisomers of the final adduct by introducing subtle changes in the general (R,R)‐configured bifunctional tertiary amine/squaramide catalyst structure. Moreover, this methodology is also amenable to a three‐component one‐pot procedure, leading to the formation of the same adducts with very good results directly from commercially available reagents, on a multigram scale, and employing a very low catalyst loading. Furthermore, a detailed experimental and computational study is described which shows the origin of the diastereodivergent behaviour of these structurally similar catalysts and the nature of the substrate–catalyst interaction.magnified image
• Investigation of lipase-catalyzed Michael-type carbon–carbon bond formations
  作者：Gernot A. Strohmeier、Tanja Sović、Georg Steinkellner、Franz S. Hartner、Aleksandra Andryushkova、Thomas Purkarthofer、Anton Glieder、Karl Gruber、Herfried Griengl

  DOI：10.1016/j.tet.2009.05.042

  日期：2009.7

  Conjugate additions of carbon nucleophiles to appropriate acceptor molecules were investigated with respect to the synthetic potential and stereochemistry of the products. Reactions of short-chain alpha,beta-unsaturated ketones and mono-substituted nitroalkenes with CH-acidic carboxylic ester derivatives were catalyzed by various immobilized lipases. Using methyl nitroacelate complete conversion with methyl vinyl ketone and trans-beta-nitrostyrene was obtained. The reactions proceeded without enantioselectivity. Evidence for enzyme catalysis is provided by the observation that after denaturation of Candida antarctica lipase B or inhibition no reaction took place. Docking studies with the chiral addition product rnethyl 2-methyl-2-nitro-5-oxoliexatioate did not reveal any specific binding mode for this reaction product, which would have been the requirement for stereoselective additions. These results support the experimental findings that the conjugate addition takes place without enantiopreference. (C) 2009 Elsevier Ltd. All rights reserved.