2-<3-(benzoyloxy)-2-nitropropyl>-1,3-dioxolane | 144001-45-6

• 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: 2-<3-(benzoyloxy)-2-nitropropyl>-1,3-dioxolane
• 英文别名: [3-(1,3-Dioxolan-2-yl)-2-nitropropyl] benzoate
• CAS: 144001-45-6
• 化学式: C₁₃H₁₅NO₆
• 分子量: 281.265
• InChiKey: MUJOQWVFFFJFEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  90.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-4-(benzylamino)-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-pentenoic acid ethyl ester 、 2-<3-(benzoyloxy)-2-nitropropyl>-1,3-dioxolane 以 乙醇 为溶剂， 反应 48.0h， 以76%的产率得到1-benzyl-2α-<<<(1,1-dimethylethyl)dimethylsilyl>oxy>methyl>-4β-<(1,3-dioxolan-2-yl)methyl>-4α-nitro-3β-pyrrolidineacetic acid ethyl ester
  参考文献：
  名称：

  A new approach to kainoids through tandem Michael reaction methodology: application to the enantioselective synthesis of (+)- and (-)-.alpha.-allokainic acid and to the formal synthesis of (-)-.alpha.-kainic acid

  摘要：

  A convergent, one-pot construction of functionalized pyrrolidine ring systems has been developed. The method is based on a tandem Michael reaction initiated by an intermolecular conjugate addition of a nitrogen nucleophile to an electrophilic olefin followed by trapping of the generated enolate by a built-in alpha,beta-unsaturated acceptor. After model studies verified the feasibility of the process and gave information about its stereochemical outcome, the strategy was successfully applied to kainoid synthesis. The construction of the basic pyrrolidine skeleton of all the members of the family requires coupling of a suitable electrophilic subunit with a common donor-acceptor fragment containing the nitrogen nucleophile. Thus, the enantioselective synthesis of (+)-alpha-allokainic acid (2) and the formal synthesis of its C-4 epimer (-)-alpha-kainic acid (1), have been accomplished using methyl vinyl ketone and 2-nitro-3-methyl-1,3-butadiene, respectively, as electrophilic partners of (S)-4-(benzylamino)-5-hydroxy-2-pentenoic acid ethyl ester (17), easily derived in six steps from D-serine. Although the acetyl group of methyl vinyl ketone is a logical precursor to the isopropenyl moiety of 2, the use of the nitrobutadiene is more appropriate for the synthesis of 1 because of the startling degree of control of the cyclization stereochemistry exerted by the nitro group.

  DOI：

  10.1021/jo00049a040
• 作为产物：
  描述：

  苯甲酰氯 、 2-(2-nitro-3-hydroxypropyl)-1,3-dioxolane 以 苯 为溶剂， 反应 24.0h， 以64%的产率得到2-<3-(benzoyloxy)-2-nitropropyl>-1,3-dioxolane
  参考文献：
  名称：

  A new approach to kainoids through tandem Michael reaction methodology: application to the enantioselective synthesis of (+)- and (-)-.alpha.-allokainic acid and to the formal synthesis of (-)-.alpha.-kainic acid

  摘要：

  A convergent, one-pot construction of functionalized pyrrolidine ring systems has been developed. The method is based on a tandem Michael reaction initiated by an intermolecular conjugate addition of a nitrogen nucleophile to an electrophilic olefin followed by trapping of the generated enolate by a built-in alpha,beta-unsaturated acceptor. After model studies verified the feasibility of the process and gave information about its stereochemical outcome, the strategy was successfully applied to kainoid synthesis. The construction of the basic pyrrolidine skeleton of all the members of the family requires coupling of a suitable electrophilic subunit with a common donor-acceptor fragment containing the nitrogen nucleophile. Thus, the enantioselective synthesis of (+)-alpha-allokainic acid (2) and the formal synthesis of its C-4 epimer (-)-alpha-kainic acid (1), have been accomplished using methyl vinyl ketone and 2-nitro-3-methyl-1,3-butadiene, respectively, as electrophilic partners of (S)-4-(benzylamino)-5-hydroxy-2-pentenoic acid ethyl ester (17), easily derived in six steps from D-serine. Although the acetyl group of methyl vinyl ketone is a logical precursor to the isopropenyl moiety of 2, the use of the nitrobutadiene is more appropriate for the synthesis of 1 because of the startling degree of control of the cyclization stereochemistry exerted by the nitro group.

  DOI：

  10.1021/jo00049a040