4-methyl-1-oxopentan-2-yl 4-nitrobenzoate | 1453495-79-8

• 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: 4-methyl-1-oxopentan-2-yl 4-nitrobenzoate
• CAS: 1453495-79-8
• 化学式: C₁₃H₁₅NO₅
• 分子量: 265.266
• InChiKey: MALAYASMEFUFBK-UHFFFAOYSA-N

物化性质

• 沸点：
  412.6±30.0 °C(Predicted)
• 密度：
  1.206±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.37
• 重原子数：
  19.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  86.51
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  4-methyl-1-oxopentan-2-yl 4-nitrobenzoate 、 2-氧代-4-苯基-3-丁酸甲酯 在 (5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以63%的产率得到(3S,4S)-methyl 3-isobutyl-2-oxo-4-phenyl-3,4-dihydro-2H-pyran-6-carboxylate
  参考文献：
  名称：

  Enantioselective NHC-catalysed redox [4+2]-hetero-Diels-Alder reactions using α-aroyloxyaldehydes and unsaturated ketoesters

  摘要：

  N-Heterocyclic carbene (NHC)-catalysed redox [4+2]-hetero-Diels-Alder reactions of alpha-aroyloxyaldehydes with either beta,gamma-unsaturated alpha-ketoesters or alpha,beta-unsaturated gamma-ketoesters generates substituted syn-dihydropyranones in good yield with excellent enantioselectivity (up to >99:1 er). The product diastereoselectivity is markedly dependent upon the nature of the unsaturated enone substituent. The presence of either electron-neutral or electron-rich aryl substituents gives excellent diastereoselectivity (up to >99:5 dr), while electron-deficient aryl substituents give reduced diastereoselectivity. In these cases, the syn-dihydropyranone products are more susceptible to base-promoted epimerisation at the C(4)-position under the reaction conditions, accounting for the lower diastereoselectivity obtained. (C) 2017 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2017.01.002
• 作为产物：
  描述：

  5-methylhex-1-en-3-yl 4-nitrobenzoate 在 臭氧 作用下， 以 二氯甲烷 为溶剂， 以56%的产率得到4-methyl-1-oxopentan-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

• 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。