(+/-)-(3S*,4S*)-tert-butyl 3-(2,3-dimethylbut-2-enyl)-4-phenylisoxazolidine-2-carboxylate

• 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: (+/-)-(3S*,4S*)-tert-butyl 3-(2,3-dimethylbut-2-enyl)-4-phenylisoxazolidine-2-carboxylate
• 英文别名: tert-butyl (3S,4S)-3-(2,3-dimethylbut-2-enyl)-4-phenyl-1,2-oxazolidine-2-carboxylate
• 化学式: C₂₀H₂₉NO₃
• 分子量: 331.455
• InChiKey: MEDFRNQVWHWXKT-ROUUACIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-溴-3-甲基-2-丁烯 、 (+/-)-tert-butyl 2-phenylbut-3-enyloxycarbamate 在 tris(dibenzylideneacetone)dipalladium (0) 、 sodium t-butanolate 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 甲苯 为溶剂， 反应 7.0h， 以65%的产率得到(+/-)-(3S*,4S*)-tert-butyl 3-(2,3-dimethylbut-2-enyl)-4-phenylisoxazolidine-2-carboxylate
  参考文献：
  名称：

  Influence of Hydroxylamine Conformation on Stereocontrol in Pd-Catalyzed Isoxazolidine-Forming Reactions

  摘要：

  Palladium-catalyzed carboamination reactions between N-Boc-O-(but-3-enyl)hydroxylamine derivatives and aryl or alkenyl bromides afford cis-3,5- and trans-4,5-disubstituted isoxazolidines in good yield with up to >20:1 dr. The diastercoselectivity observed in the formation of cis-3,5-disubstituted isoxazolidines is superior to selectivities typically obtained in other transformations, such as 1,3-dipolar cycloaddition reactions, that provide these products. In addition, the stereocontrol in the C-N bond-forming Pd-catalyzed carboamination reactions of N-Boc-O-(but-3-enyl)hydroxylamines is significantly higher than that of related C-O bond-forming carboetherification reactions of N-benzyl-N-(but-3-enyl)hydroxylamine derivatives. This is likely due to a stereoelectronic preference for cyclization via transition states in which the Boc group is placed in a perpendicular orientation relative to the plane of the developing ring, which derives from the conformational equilibria of substituted hydroxylamines.

  DOI：

  10.1021/jo8027399