5-hexynyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate | 253882-00-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 5-hexynyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• 英文别名: Hex-5-ynyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• CAS: 253882-00-7
• 化学式: C₁₄H₂₃NO₃
• 分子量: 253.342
• InChiKey: AZVSTGRLRHWYTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-hexynyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 仲丁基锂 、 三乙胺 、 鹰爪豆碱 作用下， 以 乙醚 为溶剂， 反应 24.0h， 生成 2,2,4,4-Tetramethyl-oxazolidine-3-carboxylic acid 6-phenyl-hexa-4,5-dienyl ester
  参考文献：
  名称：

  (−)-Sparteine-Mediated Stereoselective Intramolecular Carbolithiation of 4-Substituted 5-Hexynyl Carbamates. Synthesis of Enantiopure 1,3-Difunctionalized Alkylidene Cyclopentanes

  摘要：

  The stereoselective carbolithiation of alkynes with external chiral induction has been achieved for the first time by fusing the concepts of the asymmetric deprotonation (A) with s-BuLi/(-)-sparteine (s-BuLi/1) and the intramolecular carbolithiation (B). Several 4-functionalized 5-hexynyl carbamates with different terminal substituents have been prepared and efficiently cyclized providing enantiopure highly substituted alkylidene cyclopentanes. The presence of a sterically demanding substituent in the propargylic position is the essential feature of these cyclizations in order to suppress the abstraction of the remaining propargylic proton. Furthermore, in dependence on the terminal substituent, the 6-phenyl-substituted precursors undergo an intramolecular carbolithiation whereas for the 6-trimethylsilyl-substituted alkynes a sub sequent migration of the O-carbamoyl group onto the vinylic carbanionic center follows.

  DOI：

  10.1021/jo991095u
• 作为产物：
  描述：

  6,6-dibromo-5-hexynyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到5-hexynyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  (−)-Sparteine-Mediated Stereoselective Intramolecular Carbolithiation of 4-Substituted 5-Hexynyl Carbamates. Synthesis of Enantiopure 1,3-Difunctionalized Alkylidene Cyclopentanes

  摘要：

  The stereoselective carbolithiation of alkynes with external chiral induction has been achieved for the first time by fusing the concepts of the asymmetric deprotonation (A) with s-BuLi/(-)-sparteine (s-BuLi/1) and the intramolecular carbolithiation (B). Several 4-functionalized 5-hexynyl carbamates with different terminal substituents have been prepared and efficiently cyclized providing enantiopure highly substituted alkylidene cyclopentanes. The presence of a sterically demanding substituent in the propargylic position is the essential feature of these cyclizations in order to suppress the abstraction of the remaining propargylic proton. Furthermore, in dependence on the terminal substituent, the 6-phenyl-substituted precursors undergo an intramolecular carbolithiation whereas for the 6-trimethylsilyl-substituted alkynes a sub sequent migration of the O-carbamoyl group onto the vinylic carbanionic center follows.

  DOI：

  10.1021/jo991095u