dimethyl 2-methoxy-2-(2-propynyl)malonate | 507471-59-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: dimethyl 2-methoxy-2-(2-propynyl)malonate
• 英文别名: dimethyl 2-methoxy-2-(prop-2-yn-1-yl)malonate；Dimethyl 2-methoxy-2-prop-2-ynylpropanedioate
• CAS: 507471-59-2
• 化学式: C₉H₁₂O₅
• 分子量: 200.191
• InChiKey: PNULXEGOWASAGL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl 2-methoxy-2-(2-propynyl)malonate 在 氢氧化钾 作用下， 以 甲醇 、 水 为溶剂， 反应 4.0h， 生成 (+/-)-2-methoxy-4-pentynoic acid
  参考文献：
  名称：

  Synthesis of Intramolecularly Activated Lactenediynes and Evaluation of Their Activity Against Plasmid DNA

  摘要：

  The synthesis of new "selectively activated" enediyne prodrugs is reported. These compounds, belonging to the "lactenediyne" family, each possess a protected primary amine tethered at the beta-lactam nitrogen. This, once deblocked, can act as a trigger, provoking a cascade of events probably terminating with Bergman cycloaromatization of the enediyne moiety. In vitro experiments on plasmid DNA have shown that the protected compounds are inactive, while the unprotected amine is able to provoke single-strand scissions. These results open the way towards development of enzymatically activated lactenediyne prodrugs.

  DOI：

  10.1002/1099-0690(200211)2002:22<3745::aid-ejoc3745>3.0.co;2-c
• 作为产物：
  描述：

  甲氧基马来酸二甲酯 、 3-溴丙炔 在 正丁基锂 作用下， 以 正己烷 、 叔丁醇 、 甲苯 为溶剂， 反应 20.25h， 以84%的产率得到dimethyl 2-methoxy-2-(2-propynyl)malonate
  参考文献：
  名称：

  Synthesis of Intramolecularly Activated Lactenediynes and Evaluation of Their Activity Against Plasmid DNA

  摘要：

  The synthesis of new "selectively activated" enediyne prodrugs is reported. These compounds, belonging to the "lactenediyne" family, each possess a protected primary amine tethered at the beta-lactam nitrogen. This, once deblocked, can act as a trigger, provoking a cascade of events probably terminating with Bergman cycloaromatization of the enediyne moiety. In vitro experiments on plasmid DNA have shown that the protected compounds are inactive, while the unprotected amine is able to provoke single-strand scissions. These results open the way towards development of enzymatically activated lactenediyne prodrugs.

  DOI：

  10.1002/1099-0690(200211)2002:22<3745::aid-ejoc3745>3.0.co;2-c

文献信息

• Gold‐Catalyzed Desymmetric Lactonization of Alkynylmalonic Acids Enabled by Chiral Bifunctional P,N ligands
  作者：Bijin Lin、Tilong Yang、Dequan Zhang、Yang Zhou、Liangliang Wu、Jingfei Qiu、Gen‐Qiang Chen、Chi‐Ming Che、Xumu Zhang

  DOI：10.1002/anie.202201739

  日期：2022.6.7

  The gold-catalyzed desymmetrization of alkynylmalonic acids proceed smoothly to give chiral lactones with high yield and ee. Control experiments and DFT calculations indicate that the amino group of the ligands and the alcohol additives play key roles in the control of enantioselectivity.

  金催化的炔基丙二酸去对称化反应顺利进行，得到高收率和ee的手性内酯。对照实验和 DFT 计算表明，配体的氨基和醇添加剂在对映选择性的控制中起关键作用。
• Synthesis of Intramolecularly Activated Lactenediynes and Evaluation of Their Activity Against Plasmid DNA
  作者：Luca Banfi、Giuseppe Guanti

  DOI：10.1002/1099-0690(200211)2002:22<3745::aid-ejoc3745>3.0.co;2-c

  日期：2002.11

  The synthesis of new "selectively activated" enediyne prodrugs is reported. These compounds, belonging to the "lactenediyne" family, each possess a protected primary amine tethered at the beta-lactam nitrogen. This, once deblocked, can act as a trigger, provoking a cascade of events probably terminating with Bergman cycloaromatization of the enediyne moiety. In vitro experiments on plasmid DNA have shown that the protected compounds are inactive, while the unprotected amine is able to provoke single-strand scissions. These results open the way towards development of enzymatically activated lactenediyne prodrugs.