1-oxopropan-2-yl 4-nitrobenzoate | 212504-17-1

• 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: 1-oxopropan-2-yl 4-nitrobenzoate
• CAS: 212504-17-1
• 化学式: C₁₀H₉NO₅
• 分子量: 223.185
• InChiKey: FTTFZKYIKPAHNJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 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-mesityl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium tetrafluoroborate 、 1-oxopropan-2-yl 4-nitrobenzoate 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以12%的产率得到3-(1-hydroxy-2-(4-nitrophenoxy)propyl)-2-mesityl-6,7-dihydro-5H-pyrrolo[2,1-c][1,2,4]triazol-2-ium tetrafluoroborate
  参考文献：
  名称：

  Stereospecific Asymmetric N-Heterocyclic Carbene (NHC)-Catalyzed Redox Synthesis of Trifluoromethyl Dihydropyranones and Mechanistic Insights

  摘要：

  N-Heterocyclic carbene (NHC)-catalyzed redox asymmetric hetero-Diels-Alder reactions of alpha-aroyloxyaldehydes with beta-trifluoromethyl enones generates synthetically useful dihydropyranones containing a stereogenic trifluoromethyl substituent in good yields (up to 81%) and excellent diastereoselectivity and enantioselectivity (up to >95:5 dr and >99% ee). The process is stereospecific, with use of either (E)- or (Z)-beta-trifluoromethyl enones forming syn- or anti-dihydropyranone products, respectively. Mechanistic studies through in situ kinetic analysis of the reaction reveal key differences in reactivity between chiral NHC precursor 1 and an achiral NHC precursor.

  DOI：

  10.1021/jo401433q
• 作为产物：
  描述：

  丙醛 、 对硝基苯甲酸 在 哌啶 、 叔丁基过氧化氢 、 四丁基碘化铵 作用下， 以 癸烷 、 乙酸乙酯 为溶剂， 反应 5.0h， 以78%的产率得到1-oxopropan-2-yl 4-nitrobenzoate
  参考文献：
  名称：

  Stereospecific Asymmetric N-Heterocyclic Carbene (NHC)-Catalyzed Redox Synthesis of Trifluoromethyl Dihydropyranones and Mechanistic Insights

  摘要：

  N-Heterocyclic carbene (NHC)-catalyzed redox asymmetric hetero-Diels-Alder reactions of alpha-aroyloxyaldehydes with beta-trifluoromethyl enones generates synthetically useful dihydropyranones containing a stereogenic trifluoromethyl substituent in good yields (up to 81%) and excellent diastereoselectivity and enantioselectivity (up to >95:5 dr and >99% ee). The process is stereospecific, with use of either (E)- or (Z)-beta-trifluoromethyl enones forming syn- or anti-dihydropyranone products, respectively. Mechanistic studies through in situ kinetic analysis of the reaction reveal key differences in reactivity between chiral NHC precursor 1 and an achiral NHC precursor.

  DOI：

  10.1021/jo401433q

文献信息

• Enantioselective NHC‐Catalyzed Redox [2+2] Cycloadditions with Perfluoroketones: A Route to Fluorinated Oxetanes
  作者：Alyn T. Davies、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1002/chem.201504256

  日期：2015.12.21

  carbene (NHC) catalyzed redox formal [2+2] cycloaddition between α‐aroyloxyaldehydes and perfluoroketones, followed by ring‐opening in situ delivers a variety of perfluorinated β‐hydroxycarbonyl compounds in good yield, and excellent diastereo‐ and enantioselectivity. Through a reductive work‐up and subsequent cyclization, this protocol offers access to highly substituted fluorinated oxetanes in two

  N-杂环卡宾（NHC）催化α-芳酰氧基醛与全氟酮之间的氧化还原形式[2 + 2]环加成反应，然后原位开环提供各种全氟β-羟基羰基化合物，收率高，非对映和对映选择性优异。通过还原后处理和随后的环化，该方案可分两步以高ee值获得高度取代的氟化氧杂环丁烷。
• N- to C-sulfonyl photoisomerisation of dihydropyridinones: a synthetic and mechanistic study
  作者：Pei-Pei Yeh、James E. Taylor、Daniel G. Stark、David S. B. Daniels、Charlene Fallan、John C. Walton、Andrew D. Smith

  DOI：10.1039/c7ob01699a

  日期：——

  The scope and limitations of a photoinitiated N- to C-sulfonyl migration process within a range of dihydropyridinones is assessed. This sulfonyl transfer proceeds without erosion of either diastereo- or enantiocontrol, and is general across a range of N-sulfonyl substituents (SO2R; R = Ph, 4-MeC6H4, 4-MeOC6H4, 4-NO2C6H4, Me, Et) as well as C(3)-(aryl, heteroaryl, alkyl and alkenyl) and C(4)-(aryl and

  评估了在二氢吡啶酮类化合物中光引发的N-到C-磺酰基迁移过程的范围和局限性。此磺酰转让收益而无需任diastereo-或enantiocontrol的侵蚀，并在一系列的是一般ñ -磺酰基的取代基（SO 2 R等R = PH，4-MEC 6 ħ 4，4-MeOC 6 H ^ 4，4-NO 2 C 6 H 4，Me，Et）以及C（3）-（芳基，杂芳基，烷基和烯基）和C（4）-（芳基和酯）取代。交叉反应表明分子间步骤在正式的迁移过程中是可操作的，尽管未观察到与C-磺酰基产物的交叉。EPR研究表明，磺酰基的中间体，并基于这些观察结果提出了一种机理。
• NHC-catalyzed enantioselective synthesis of β-trifluoromethyl-β-hydroxyamides
  作者：Alyn T Davies、Mark D Greenhalgh、Alexandra M Z Slawin、Andrew D Smith

  DOI：10.3762/bjoc.16.129

  日期：——

  The N-heterocyclic carbene (NHC)-catalyzed formal [2 + 2] cycloaddition between α-aroyloxyaldehydes and trifluoroacetophenones, followed by ring opening with an amine or a reducing agent is described. The resulting β-trifluoromethyl-β-hydroxyamide and alcohol products are produced with reasonable diastereocontrol (typically ≈70:30 dr) and excellent enantioselectivity, and they can be isolated in moderate

  描述了在α-芳酰氧基醛和三氟苯乙酮之间进行N-杂环卡宾（NHC）催化的甲醛[2 + 2]环加成反应，然后用胺或还原剂进行开环。生成的β-三氟甲基-β-羟基酰胺和醇产物具有合理的非对映异构控制（通常≈70:30 dr）和出色的对映选择性，可以作为单一非对映异构体以中等至良好的收率分离。
• Asymmetric NHC-Catalyzed Redox α-Amination of α-Aroyloxyaldehydes
  作者：James E. Taylor、David S. B. Daniels、Andrew D. Smith

  DOI：10.1021/ol402955f

  日期：2013.12.6

  (NHC)-catalyzed redox reaction of α-aroyloxyaldehydes with N-aryl-N-aroyldiazenes to form α-hydrazino esters with high enantioselectivity (up to 99% ee) is reported. The hydrazide products are readily converted into enantioenriched N-aryl amino esters through samarium(II) iodide mediated N–N bond cleavage.

  报道了通过 N-杂环卡宾 (NHC) 催化的 α-芳酰氧基醛与N-芳基-N-芳酰基二氮烯的氧化还原反应形成具有高对映选择性（高达 99% ee）的 α-肼基酯的不对称 α-胺化。通过碘化钐（II）介导的 N-N 键断裂，酰肼产物很容易转化为对映体富集的N-芳基氨基酯。
• Enantioselective N-heterocyclic carbene catalyzed formal [3+2] cycloaddition using α-aroyloxyaldehydes and oxaziridines
  作者：Ryan W.F. Kerr、Mark D. Greenhalgh、Alexandra M.Z. Slawin、Polly L. Arnold、Andrew D. Smith

  DOI：10.1016/j.tetasy.2016.10.012

  日期：2017.1

  An enantioselective N-heterocyclic carbene catalysed formal [3+2] cycloaddition has been developed for the synthesis of oxazolindin-4-one products. The reaction of oxaziridines and alpha-aroyloxyaldehydes under N-heterocyclic carbene catalysis provides the formal cycloaddition products with excellent control of the diastereo- and enantioselectivity (12 examples, up to >95:5 dr, >99:1 er). A matched-mismatched effect between the enantiomer of the catalyst and oxaziridine was identified, and preliminary mechanistic studies have allowed the proposal of a model to explain these observations. (C) 2016 Published by Elsevier Ltd.