3,6-bis(ethoxycarbonyl)-2-ethoxy-4-methylpyridine | 141903-26-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 3,6-bis(ethoxycarbonyl)-2-ethoxy-4-methylpyridine
• 英文别名: Diethyl 6-ethoxy-4-methylpyridine-2,5-dicarboxylate
• CAS: 141903-26-6
• 化学式: C₁₄H₁₉NO₅
• 分子量: 281.309
• InChiKey: QYSUOEDDMTWXLU-UHFFFAOYSA-N

物化性质

• 沸点：
  395.3±37.0 °C(Predicted)
• 密度：
  1.133±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  74.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,6-bis(ethoxycarbonyl)-2-ethoxy-4-methylpyridine 在 乙醇 、 potassium tert-butylate 、 四丁基碘化铵 、 sodium hydride 、 potassium carbonate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.19h， 生成 9-(benzyloxy)-8-cyano-1-ethoxy-3-(ethoxycarbonyl)-7,8-dihydro-6H-cyclopentisoquinoline
  参考文献：
  名称：

  Total Synthesis of Natural and ent-Fredericamycin A

  摘要：

  A total synthesis of both enantiomers of the potent antitumor-antibiotic fredericamycin A (1) is detailed based on a room temperature inverse electron demand Diels-Alder reaction of a N-sulfonyl-1-aza-1,3-butadiene for assemblage of a pyridone F ring precursor, a single-step Michael addition-intramolecular acylation for annulation of the DE ring system onto this pyridone F ring precursor, implementation of a regiospecific chromium carbene benzannulation reaction for AB ring construction, and a simple aldol closure for introduction of the spiro CD ring system. Resolution of the penultimate precursor 41 followed by deprotection provided natural and ent-fredericamycin A. The indistinguishable cytotoxic potency of the two enantiomers (L1210 IC50, 0.03 and 0.04 mu g/mL, respectively) is disclosed along with that of the key partial structures 2 (IC50 = 2 mu g/mL) and 21 IC50 = 7 mu g/mL) constituting the fully functionalized ABCDE and DEF ring systems of the natural product.

  DOI：

  10.1021/ja00153a004
• 作为产物：
  描述：

  ethyl (E)-2-<(methylsulfonyl)imino>-3-pentenoate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 25.0~70.0 ℃ 、1300.0 MPa 条件下， 反应 73.0h， 生成 3,6-bis(ethoxycarbonyl)-2-ethoxy-4-methylpyridine
  参考文献：
  名称：

  A concise synthesis of the fredericamycin A DEF ring system: [4 + 2] cycloaddition reactions of 1-aza-1,3-butadienes

  摘要：

  A concise four-step synthesis of the fredericamycin A DEF ring system is detailed based on the LUMO(diene)-controlled Diels-Alder reaction of N-sulfonyl-1-azadiene 3 for introduction of the pyridone F ring.

  DOI：

  10.1021/jo00040a044

文献信息

• Total Synthesis of Natural and ent-Fredericamycin A
  作者：Dale L. Boger、Ottmar Hueter、Kapiamba Mbiya、Minsheng Zhang

  DOI：10.1021/ja00153a004

  日期：1995.12

  A total synthesis of both enantiomers of the potent antitumor-antibiotic fredericamycin A (1) is detailed based on a room temperature inverse electron demand Diels-Alder reaction of a N-sulfonyl-1-aza-1,3-butadiene for assemblage of a pyridone F ring precursor, a single-step Michael addition-intramolecular acylation for annulation of the DE ring system onto this pyridone F ring precursor, implementation of a regiospecific chromium carbene benzannulation reaction for AB ring construction, and a simple aldol closure for introduction of the spiro CD ring system. Resolution of the penultimate precursor 41 followed by deprotection provided natural and ent-fredericamycin A. The indistinguishable cytotoxic potency of the two enantiomers (L1210 IC50, 0.03 and 0.04 mu g/mL, respectively) is disclosed along with that of the key partial structures 2 (IC50 = 2 mu g/mL) and 21 IC50 = 7 mu g/mL) constituting the fully functionalized ABCDE and DEF ring systems of the natural product.
• A concise synthesis of the fredericamycin A DEF ring system: [4 + 2] cycloaddition reactions of 1-aza-1,3-butadienes
  作者：Dale L. Boger、Minsheng Zhang

  DOI：10.1021/jo00040a044

  日期：1992.7

  A concise four-step synthesis of the fredericamycin A DEF ring system is detailed based on the LUMO(diene)-controlled Diels-Alder reaction of N-sulfonyl-1-azadiene 3 for introduction of the pyridone F ring.