2'-[(1R)-1-phenylethyl]spiro[bicyclo[2.2.1]heptane-2,3'-oxaziridine] | 83324-06-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 2'-[(1R)-1-phenylethyl]spiro[bicyclo[2.2.1]heptane-2,3'-oxaziridine]
• CAS: 83324-06-5
• 化学式: C₁₅H₁₉NO
• 分子量: 229.322
• InChiKey: INAMEFNWCMBSMV-FFDOZHHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  15.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2'-[(1R)-1-phenylethyl]spiro[bicyclo[2.2.1]heptane-2,3'-oxaziridine] 以32%的产率得到2-[(1R)-1-phenylethyl]-2-azabicyclo[3.2.1]octan-3-one
  参考文献：
  名称：

  Syntheses and rearrangements of spirocyclic oxaziridines derived from unsymmetrical ketones

  摘要：

  Oxaziridines provide useful alternatives to the Beckmann rearrangement and Schmidt reaction for ring enlargement of cyclic ketones. The procedure involves the condensation of the ketone in question with optically active alpha-methylbenzylamine, oxidation of the resultant imine, and photolysis to afford ring-expanded lactams. The alpha-phenylethyl substituent can be removed after photolysis to yield the N-unsubstituted lactam. When a distal ketone substituent is present, the oxaziridines can be synthesized stereoselectively. Thus, optically active ketones can be converted to either ring-expanded lactam by choice of either enantiomer of optically active alpha-methylbenzylamine. Ketones bearing adjacent substitution are generally not amenable to such regiocontrol because the resident substituent is the key stereocontrol element for the oxaziridine synthesis, although a notable exception is 2-methoxycyclohexanone. Stereogenic centers present in such compounds undergo epimerization during the couse of the reaction sequence; in addition, substrates containing substantial amounts of enamine give rise to novel doubly oxygenated products upon oxidation. Finally, the conformational behavior of the side chains in both oxaziridines and their product lactams permits some key stereochemical assignments to be made, on the basis of chemical shift trends in the NMR spectra of these materials.

  DOI：

  10.1021/jo00002a006
• 作为产物：
  描述：

  降樟脑 、 R(+)-alpha-甲基苄胺 在 间氯过氧苯甲酸 作用下， 生成 2'-[(1R)-1-phenylethyl]spiro[bicyclo[2.2.1]heptane-2,3'-oxaziridine]
  参考文献：
  名称：

  Syntheses and rearrangements of spirocyclic oxaziridines derived from unsymmetrical ketones

  摘要：

  Oxaziridines provide useful alternatives to the Beckmann rearrangement and Schmidt reaction for ring enlargement of cyclic ketones. The procedure involves the condensation of the ketone in question with optically active alpha-methylbenzylamine, oxidation of the resultant imine, and photolysis to afford ring-expanded lactams. The alpha-phenylethyl substituent can be removed after photolysis to yield the N-unsubstituted lactam. When a distal ketone substituent is present, the oxaziridines can be synthesized stereoselectively. Thus, optically active ketones can be converted to either ring-expanded lactam by choice of either enantiomer of optically active alpha-methylbenzylamine. Ketones bearing adjacent substitution are generally not amenable to such regiocontrol because the resident substituent is the key stereocontrol element for the oxaziridine synthesis, although a notable exception is 2-methoxycyclohexanone. Stereogenic centers present in such compounds undergo epimerization during the couse of the reaction sequence; in addition, substrates containing substantial amounts of enamine give rise to novel doubly oxygenated products upon oxidation. Finally, the conformational behavior of the side chains in both oxaziridines and their product lactams permits some key stereochemical assignments to be made, on the basis of chemical shift trends in the NMR spectra of these materials.

  DOI：

  10.1021/jo00002a006

文献信息

• Syntheses and rearrangements of spirocyclic oxaziridines derived from unsymmetrical ketones
  作者：Jeffrey Aube、Marlys Hammond、Elyse Gherardini、Fusao Takusagawa

  DOI：10.1021/jo00002a006

  日期：1991.1

  Oxaziridines provide useful alternatives to the Beckmann rearrangement and Schmidt reaction for ring enlargement of cyclic ketones. The procedure involves the condensation of the ketone in question with optically active alpha-methylbenzylamine, oxidation of the resultant imine, and photolysis to afford ring-expanded lactams. The alpha-phenylethyl substituent can be removed after photolysis to yield the N-unsubstituted lactam. When a distal ketone substituent is present, the oxaziridines can be synthesized stereoselectively. Thus, optically active ketones can be converted to either ring-expanded lactam by choice of either enantiomer of optically active alpha-methylbenzylamine. Ketones bearing adjacent substitution are generally not amenable to such regiocontrol because the resident substituent is the key stereocontrol element for the oxaziridine synthesis, although a notable exception is 2-methoxycyclohexanone. Stereogenic centers present in such compounds undergo epimerization during the couse of the reaction sequence; in addition, substrates containing substantial amounts of enamine give rise to novel doubly oxygenated products upon oxidation. Finally, the conformational behavior of the side chains in both oxaziridines and their product lactams permits some key stereochemical assignments to be made, on the basis of chemical shift trends in the NMR spectra of these materials.