ethyl 2-acetyl-2-methyl-4-nitro-3-phenylbutanoate

• 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: ethyl 2-acetyl-2-methyl-4-nitro-3-phenylbutanoate
• 化学式: C₁₅H₁₉NO₅
• 分子量: 293.32
• InChiKey: LCKZUJVPWRYQRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  89.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2-甲基乙酰乙酸乙酯 、 反式硝基苯乙烯 在 三乙烯二胺 作用下， 以 neat (no solvent) 为溶剂， 生成 ethyl 2-acetyl-2-methyl-4-nitro-3-phenylbutanoate
  参考文献：
  名称：

  Supported bifunctional thioureas as recoverable and reusable catalysts for enantioselective nitro-Michael reactions

  摘要：

  不同支撑的双官能硫脲在磺酰基聚苯乙烯树脂上的催化活性已经在不同亲核试剂对反式-β-硝基苯乙烯衍生物的硝基迈克尔加成中进行了研究。催化剂的活性取决于将手性硫脲与聚合物连接的链长度。最佳结果是使用由(L)-缬氨酸和1,6-己二胺衍生的硫脲得到的。催化剂可以在仅2%的负载下使用，并在纯净条件下至少重复使用四个周期。球磨促进的加成也非常有效。

  DOI：

  10.3762/bjoc.12.61

文献信息

• [EN] ASYMMETRIC MICHAEL AND ALDOL ADDITION USING BIFUNCTIONAL CINCHONA-ALKALOID-BASED CATALYSTS<br/>[FR] ADDITIONS ASYMETRIQUES DE MICHAEL ET D'ALDOL UTILISANT DES CATALYSEURS BIFONCTIONNELS A BASE DE CINCHONINE
  申请人：UNIV BRANDEIS

  公开号：WO2005121137A1

  公开（公告）日：2005-12-22

  One aspect of the present invention relates to quinine-based and quinidine-based catalysts. Another aspect of the invention relates to a method of preparing a derivatized quinine-based or quinidine-based catalyst comprising 1) reacting quinine or quinidine with 5 base and a compound that has a suitable leaving group, and 2) converting the ring methoxy group to a hydroxy group. Another aspect of the present invention relates to a method of preparing a chiral, non-racemic compound from a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral ketone, comprising the step of: reacting a prochiral electron-deficient alkene or azo compound or prochiral aldehyde or prochiral 10 ketone with a nucleophile in the presence of a catalyst; thereby producing a chiral, non racemic compound; wherein said catalyst is a derivatized quinine or quinidine. Another aspect of the present invention relates to a method of kinetic resolution, comprising the step of reacting racemic chiral alkene with a nucleophile in the presence of a derivatized quinine or quinidine.

  本发明的一个方面涉及基于奎宁和奎宁的催化剂。发明的另一个方面涉及一种制备衍生奎宁或奎宁催化剂的方法，包括1）将奎宁或奎宁与5碱和具有适当离去基团的化合物反应，以及2）将环甲氧基转化为羟基。本发明的另一个方面涉及一种从前手性电子亏缺烯烃或偶氮化合物或前手性醛或前手性酮制备手性、非拉克米化合物的方法，包括以下步骤：在催化剂存在下，将前手性电子亏缺烯烃或偶氮化合物或前手性醛或前手性酮与亲核试剂反应；从而产生手性、非拉克米化合物；其中所述催化剂是衍生奎宁或奎宁。本发明的另一个方面涉及一种动力学分辨的方法，包括在衍生奎宁或奎宁存在下，将拉克米手性烯烃与亲核试剂反应的步骤。
• Asymmetric generation of fluorine-containing quaternary carbons adjacent to tertiary stereocenters: uses of fluorinated methines as nucleophiles
  作者：Xiao Han、Jie Luo、Chen Liu、Yixin Lu

  DOI：10.1039/b823184b

  日期：——

  Organocatalytic asymmetric Michael reactions of fluorinated nucleophiles with nitroolefins catalyzed by Cinchona alkaloid-derived thiourea catalysts generated the desired Michael products containing vicinal fluorinated quaternary and tertiary chiral centers with exceptional enantioselectivity.

  由金鸡纳生物碱衍生的硫脲催化剂催化的氟化亲核试剂与硝基烯烃的有机催化不对称迈克尔反应生成了所需的迈克尔产物，该产物含有邻位氟化的季铵和叔手性中心，并具有出色的对映选择性。
• Catalytic Asymmetric 1,4-Additions of β-Keto Esters to Nitroalkenes Promoted by a Bifunctional Homobimetallic Co2-Schiff Base Complex
  作者：Makoto Furutachi、Zhihua Chen、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.3390/molecules15010532

  日期：——

  Catalytic asymmetric 1,4-addition of β-keto esters to nitroalkenes is described. 2.5 mol % of a homobimetallic Lewis acid/Brønsted base bifunctional Co2-Schiff base complex smoothly promoted the reaction in excellent yield (up to 99%), diastereoselectivity, and enantioselectivity (up to >30:1 dr and 98% ee). Catalyst loading was successfully reduced to 0.1 mol %. Mechanistic studies suggested that

  描述了 β-酮酯与硝基烯烃的催化不对称 1,4-加成反应。2.5 mol% 的均双金属路易斯酸/Brønsted 碱双功能 Co2-Schiff 碱配合物以优异的产率（高达 99%）、非对映选择性和对映选择性（高达 >30:1 dr 和 98% ee）顺利促进反应。催化剂负载成功地降低到 0.1 mol%。机理研究表明，两个 Co 金属中心的分子内协同功能对于高催化活性和立体选择性很重要。
• Stereocontrolled Creation of Adjacent Quaternary and Tertiary Stereocenters by a Catalytic Conjugate Addition
  作者：Hongming Li、Yi Wang、Liang Tang、Fanghui Wu、Xiaofeng Liu、Chengyun Guo、Bruce M. Foxman、Li Deng

  DOI：10.1002/anie.200461923

  日期：2005.1
• Tris-ureas as versatile and highly efficient organocatalysts for Michael addition reactions of nitro-olefins: Mechanistic insight from in-situ diagnostics
  作者：Milan Bera、Tamal Kanti Ghosh、Bidyut Akhuli、Pradyut Ghosh

  DOI：10.1016/j.molcata.2015.01.004

  日期：2015.11

  Tris(2-aminoethyl)-amine, TREN based tris-ureas (1a-1d) and tris-thiourea (1e) have been explored towards a wide range of catalytic Michael addition reactions. These tris-ureas, 1a-1d efficiently catalyze the addition reaction of beta-nitro styrenes (2a-2d) with various nucleophiles such as beta-ketoesters (3a-3c), 1,3-dicarbonyl compound (3d), a cyanoester (3e) and a nitroester (3f) under ambient conditions to produce corresponding nitro alkanes in high yields. Pentafluorophenyl attached tris-urea, 1d is found to be the most effective catalyst in the series that yields 78-98% products conversion. In case of the reaction between beta-nitro styrenes and malononitrile (3g) in presence of 1d, 2-amino-5-nitro-4,6-diphenylcyclohex-1-ene-1,3,3-tricarbonitriles are also isolated as a minor product along with the corresponding Michael adduct. The added advantage of bridge-head nitrogen center in tris-urea organocatalysts, 1a-1d has been established by studying analogous benzene platform based tris-ureas (1f, 1g, 1h) in similar experimental conditions. Furthermore, a plausible reaction mechanism has also been established based on in-situ H-1 NMR kinetic studies. (C) 2015 Elsevier B.V. All rights reserved.