ethyl 4-acetoxybut-2-ynoate | 1246080-11-4

• 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: ethyl 4-acetoxybut-2-ynoate
• CAS: 1246080-11-4
• 化学式: C₈H₁₀O₄
• 分子量: 170.165
• InChiKey: FDPHYPLWTBSEQK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.12
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  ethyl 4-acetoxybut-2-ynoate 在 三苯基膦氯金 、 水 、 silver trifluoromethanesulfonate 作用下， 以 1,4-二氧六环 为溶剂， 反应 1.0h， 以96%的产率得到4-乙酰氧基-3-氧代丁酸乙酯
  参考文献：
  名称：

  Synthesis of γ-Acetoxy β-Keto Esters Through Regioselective Hydration of γ-Acetoxy-α,β-alkynoates

  摘要：

  The At(I)-catalyzed regioselective hydration of gamma-acetoxy-alpha,beta-acetylinic ester by the assistance of a neighboring carbonyl group has beets developed. Varieties of simple primary, secondary, and tertiary gamma-acetoxy-alpha,beta-acetylinic esters, even those bearing sensitive functional group in the remote reaction sites, are selectively hydrated to the corresponding beta-keto esters. The reaction' tolerates a wide variety of other carboxylates, such as benzoates, propionates, acrylates, and pivalates, including chiral carboxylates with retention of the configuration. The broad substrate scope, including the derivatization of complex natural products and neutral and open air conditions, makes this atom economical approach very practical. O-18 labeling experiments disclose that the oxygen transposition occurs from the carboxylate group to the triple bond, not from water.

  DOI：

  10.1021/acs.joc.5b00400
• 作为产物：
  描述：

  ethyl 4-((tetrahydro-2H-pyran-2-yl)oxy)but-2-ynoate 在 4-二甲氨基吡啶 、 对甲苯磺酸 、 三乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 ethyl 4-acetoxybut-2-ynoate
  参考文献：
  名称：

  Synthesis of γ-Acetoxy β-Keto Esters Through Regioselective Hydration of γ-Acetoxy-α,β-alkynoates

  摘要：

  The At(I)-catalyzed regioselective hydration of gamma-acetoxy-alpha,beta-acetylinic ester by the assistance of a neighboring carbonyl group has beets developed. Varieties of simple primary, secondary, and tertiary gamma-acetoxy-alpha,beta-acetylinic esters, even those bearing sensitive functional group in the remote reaction sites, are selectively hydrated to the corresponding beta-keto esters. The reaction' tolerates a wide variety of other carboxylates, such as benzoates, propionates, acrylates, and pivalates, including chiral carboxylates with retention of the configuration. The broad substrate scope, including the derivatization of complex natural products and neutral and open air conditions, makes this atom economical approach very practical. O-18 labeling experiments disclose that the oxygen transposition occurs from the carboxylate group to the triple bond, not from water.

  DOI：

  10.1021/acs.joc.5b00400

文献信息

• [4+2] Cycloaddition Reactions Between 1,8-Disubstituted Cyclooctatetraenes and Diazo Dienophiles: Stereoelectronic Effects, Anticancer Properties and Application to the Synthesis of 7,8-Substituted Bicyclo[4.2.0]octa-2,4-dienes
  作者：Rebecca L. Grange、Michael J. Gallen、Heiko Schill、Jenny P. Johns、Lin Dong、Peter G. Parsons、Paul W. Reddell、Victoria A. Gordon、Paul V. Bernhardt、Craig M. Williams

  DOI：10.1002/chem.200903454

  日期：2010.8.2

  azodicarboxylate (DIAD) and 1,8‐disubstituted cyclooctatetraenes are also described and further manipulation of a resulting cycloadduct uncovered a new pathway to the synthetically challenging bicyclo[4.2.0]octa‐2,4‐diene family. Variation of the substituents resulted in a range of compounds displaying selective action against different human tumour cell types.

  对1,8-二取代的环辛酸酯与重氮化合物之间的[4 + 2]环加成反应的详细研究显示，4-苯基-1,2,4-三唑-3,5-二酮（PTAD）反应形成2,3 -或3,4-二取代的加合物。产物分布可通过调节环辛酸酯的电子密度来控制。还介绍了偶氮二羧酸二异丙酯（DIAD）与1,8-二取代的环辛酸酯之间前所未有的[4 + 2]环加成反应，对所得环加合物的进一步操作揭示了通向具有合成挑战性的双环[4.2.0] octa-2,4-的新途径二烯家族。取代基的变化导致一系列化合物显示出对不同人类肿瘤细胞类型的选择性作用。