methyl 4-N-(tert-butoxycarbamoyl)-α-nitro-2-cyclopentenylacetate | 725233-40-9

• 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
• 英文名称: methyl 4-N-(tert-butoxycarbamoyl)-α-nitro-2-cyclopentenylacetate
• 英文别名: methyl 2-[(1S,4R)-4-[(2-methylpropan-2-yl)oxycarbonylamino]cyclopent-2-en-1-yl]-2-nitroacetate
• CAS: 725233-40-9
• 化学式: C₁₃H₂₀N₂O₆
• 分子量: 300.312
• InChiKey: YNPASMFKTMJFGE-ZDGBYWQASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  110
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4-N-(tert-butoxycarbamoyl)-α-nitro-2-cyclopentenylacetate 在 盐酸 、 sodium hydroxide sodium tetrahydroborate 、 titanium(III) chloride 、 L-酒石酸 、 碳酸氢钠 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 4.75h， 生成
  参考文献：
  名称：

  Chemoenzymatic Synthesis and Synthetic Application of Enantiopure Aminocyclopentenols:  Total Synthesis of Carbocyclic (+)-Uracil Polyoxin C and Its α-Epimer

  摘要：

  Carbocyclic uracil polyoxin C (+)-2 and its alpha-epimer (-)-3 were synthesized in an efficient fashion from cis-4-(N-tert-butylcarbamoyl)cyclopent-2-en-1-ol (+/-)-7. The synthesis incorporates a concise, inexpensive chemoenzymatic synthesis of enantiopure aminocyclopentenols, a Pd(O)-catalyzed substitution reaction, and a mild reduction of an alpha-nitro ester by TiCl3/sodium borohydride. Significantly, this process demonstrates the synthetic utility of the versatile enantiopure aminocyclopentenol building block 4.

  DOI：

  10.1021/jo0496796
• 作为产物：
  描述：

  3,3a,4,6a-tetrahydro-2H-cyclopenta[d]oxazol-2-one 在 四(三苯基膦)钯 4-二甲氨基吡啶 、 sodium hydride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 4-N-(tert-butoxycarbamoyl)-α-nitro-2-cyclopentenylacetate
  参考文献：
  名称：

  Enzymatic Resolution of Aminocyclopentenols as Precursors to d- and l-Carbocyclic Nucleosides

  摘要：

  Racemic cis-4-aminocyclopent-2-en-1-ols were synthesized in three steps utilizing hetero Diels-Alder chemistry. Starting from suitably protected hydroxylamines, oxidization with sodium periodate and trapping with cyclopentadiene afforded cycloadducts (+/-)-5a-d. The N-O bond of the cycloadducts was reduced with Mo(CO)(6) to afford (+/-)-cis-4-aminocyclopent-2-en-1-ols (+/-)-6a-d. These compounds, or their corresponding acetates, were kinetically resolved by enzymatic acetylation or hydrolysis, respectively. Enzymatic acetylation of cis-N-(benzylcarbamoyl)-4-aminocyclopent-2-enol [(+/-)-6a] with Candida antarctica B lipase and Pseudomonas species lipase gave the corresponding acetate (-)-7a in 90% and 92% ee, respectively, after 40% conversion. Enzymatic hydrolysis of cis-N-acetyl-4-aminocyclopent-2-enol 1-O-acetate (+/-)-7d with electric eel acetylcholine esterase was successful in providing both cis-N-acetyl-4-aminocyclopent-2-enols (+)ed and (+)-7d in 92% ee (99% ee after a single recrystallization) after 40% conversion. Further synthetic transformations of these resolved synthetic building blocks and derivatives are also reported.

  DOI：

  10.1021/jo972265a

文献信息

• Total Synthesis of (±) Carbocyclic Polyoxin C and Its α-Epimer
  作者：Deyi Zhang、Marvin J. Miller

  DOI：10.1021/jo971711r

  日期：1998.2.1

  Carbocyclic polyoxin C (2) and its alpha-epimer 3 were synthesized in racemic form in an efficient and diastereodivergent fashion from cis-4-(N-tert-butylcarbamoyl)cyclopent-2-en-1-ol (5a). This synthesis features a Pd(0)-catalyzed substitution reaction, a novel, mild reduction of an alpha-nitro ester to an amino acid ester, and an improved procedure for uracil ring formation.

  碳环多氧化合物C（2）及其alpha-顶基3以高效和非对映异构的方式由顺式4-（N-叔丁基氨基甲酰基）环戊-2-烯-1-醇（5a）外消旋形式合成。该合成具有Pd（0）催化的取代反应，α-硝基酯向氨基酸酯的新型轻度还原以及尿嘧啶环形成的改进程序。
• Enzymatic Resolution of Aminocyclopentenols as Precursors to <scp>d</scp>- and <scp>l</scp>-Carbocyclic Nucleosides
  作者：Mark J. Mulvihill、Jennifer L. Gage、Marvin J. Miller

  DOI：10.1021/jo972265a

  日期：1998.5.1

  Racemic cis-4-aminocyclopent-2-en-1-ols were synthesized in three steps utilizing hetero Diels-Alder chemistry. Starting from suitably protected hydroxylamines, oxidization with sodium periodate and trapping with cyclopentadiene afforded cycloadducts (+/-)-5a-d. The N-O bond of the cycloadducts was reduced with Mo(CO)(6) to afford (+/-)-cis-4-aminocyclopent-2-en-1-ols (+/-)-6a-d. These compounds, or their corresponding acetates, were kinetically resolved by enzymatic acetylation or hydrolysis, respectively. Enzymatic acetylation of cis-N-(benzylcarbamoyl)-4-aminocyclopent-2-enol [(+/-)-6a] with Candida antarctica B lipase and Pseudomonas species lipase gave the corresponding acetate (-)-7a in 90% and 92% ee, respectively, after 40% conversion. Enzymatic hydrolysis of cis-N-acetyl-4-aminocyclopent-2-enol 1-O-acetate (+/-)-7d with electric eel acetylcholine esterase was successful in providing both cis-N-acetyl-4-aminocyclopent-2-enols (+)ed and (+)-7d in 92% ee (99% ee after a single recrystallization) after 40% conversion. Further synthetic transformations of these resolved synthetic building blocks and derivatives are also reported.
• Chemoenzymatic Synthesis and Synthetic Application of Enantiopure Aminocyclopentenols:  Total Synthesis of Carbocyclic (+)-Uracil Polyoxin C and Its α-Epimer
  作者：Fangzheng Li、John B. Brogan、Jennifer L. Gage、Deyi Zhang、Marvin J. Miller

  DOI：10.1021/jo0496796

  日期：2004.6.1

  Carbocyclic uracil polyoxin C (+)-2 and its alpha-epimer (-)-3 were synthesized in an efficient fashion from cis-4-(N-tert-butylcarbamoyl)cyclopent-2-en-1-ol (+/-)-7. The synthesis incorporates a concise, inexpensive chemoenzymatic synthesis of enantiopure aminocyclopentenols, a Pd(O)-catalyzed substitution reaction, and a mild reduction of an alpha-nitro ester by TiCl3/sodium borohydride. Significantly, this process demonstrates the synthetic utility of the versatile enantiopure aminocyclopentenol building block 4.