Methyl 3-[2-(3-methoxy-3-oxopropyl)sulfanyl-3-[3-(3-methoxy-3-oxopropyl)sulfanyl-2,5-dioxopyrrolidin-1-yl]propyl]sulfanylpropanoate | 1471121-92-2

• 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 3-[2-(3-methoxy-3-oxopropyl)sulfanyl-3-[3-(3-methoxy-3-oxopropyl)sulfanyl-2,5-dioxopyrrolidin-1-yl]propyl]sulfanylpropanoate
• 英文别名: methyl 3-[2-(3-methoxy-3-oxopropyl)sulfanyl-3-[3-(3-methoxy-3-oxopropyl)sulfanyl-2,5-dioxopyrrolidin-1-yl]propyl]sulfanylpropanoate
• CAS: 1471121-92-2
• 化学式: C₁₉H₂₉NO₈S₃
• 分子量: 495.639
• InChiKey: JVLNNNGCBIVMCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  31
• 可旋转键数：
  18
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  192
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为产物：
  描述：

  1-(2-丙炔-1-基)-1H-吡咯-2,5-二酮 在 安息香双甲醚 、 三乙胺 作用下， 以 氯仿 为溶剂， 反应 0.08h， 生成 Methyl 3-[2-(3-methoxy-3-oxopropyl)sulfanyl-3-[3-(3-methoxy-3-oxopropyl)sulfanyl-2,5-dioxopyrrolidin-1-yl]propyl]sulfanylpropanoate
  参考文献：
  名称：

  Experimental and Theoretical Studies of Selective Thiol–Ene and Thiol–Yne Click Reactions Involving N-Substituted Maleimides

  摘要：

  A combination of experimental and computational methods has been used to understand the reactivity and selectivity of orthogonal thiol-ene and thiol-yne "click" reactions involving N-allyl maleimide (1) and N-propargyl maleimide (2). Representative thiols methyl-3-mercaptopropionate and beta-mercaptoethanol are shown to add exclusively and quantitatively to the electron poor maleimide alkene of 1 and 2 under base (Et3N) initiated thiol-Michael conditions. Subsequent radical-mediated thiol-ene or thiol-yne reactions can be carried out to further functionalize the remaining allyl or propargyl moieties in near quantitative yields (>95%). Selectivity, however, can only be achieved when base-initiated thiol-Michael reactions are carried out first, as radical-mediated reactions between equimolar amounts of thiol and N-substituted maleimides give complex mixtures of products. CBS-QB3 calculations have been used to investigate the energetics and kinetics of reactions between a representative thiol (methyl mercaptan) with N-allyl and N-propargyl maleimide under both base-initiated and radical-mediated conditions. Calculations help elucidate the factors that underlie the selective base-initiated and nonselective radical-mediated thiol-ene/yne reactions. The results provide additional insights into how to design selective radical-mediated thiol-ene/yne reactions.

  DOI：

  10.1021/jo4014436

文献信息

• Experimental and Theoretical Studies of Selective Thiol–Ene and Thiol–Yne Click Reactions Involving <i>N</i>-Substituted Maleimides
  作者：Robert M. Stolz、Brian H. Northrop

  DOI：10.1021/jo4014436

  日期：2013.8.16

  A combination of experimental and computational methods has been used to understand the reactivity and selectivity of orthogonal thiol-ene and thiol-yne "click" reactions involving N-allyl maleimide (1) and N-propargyl maleimide (2). Representative thiols methyl-3-mercaptopropionate and beta-mercaptoethanol are shown to add exclusively and quantitatively to the electron poor maleimide alkene of 1 and 2 under base (Et3N) initiated thiol-Michael conditions. Subsequent radical-mediated thiol-ene or thiol-yne reactions can be carried out to further functionalize the remaining allyl or propargyl moieties in near quantitative yields (>95%). Selectivity, however, can only be achieved when base-initiated thiol-Michael reactions are carried out first, as radical-mediated reactions between equimolar amounts of thiol and N-substituted maleimides give complex mixtures of products. CBS-QB3 calculations have been used to investigate the energetics and kinetics of reactions between a representative thiol (methyl mercaptan) with N-allyl and N-propargyl maleimide under both base-initiated and radical-mediated conditions. Calculations help elucidate the factors that underlie the selective base-initiated and nonselective radical-mediated thiol-ene/yne reactions. The results provide additional insights into how to design selective radical-mediated thiol-ene/yne reactions.