N-tert-butoxycarbonyl-3-(2,3,5-trichlorophenyl)oxaziridine | 163226-33-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: N-tert-butoxycarbonyl-3-(2,3,5-trichlorophenyl)oxaziridine
• 英文别名: Tert-butyl 3-(2,3,5-trichlorophenyl)oxaziridine-2-carboxylate
• CAS: 163226-33-3
• 化学式: C₁₂H₁₂Cl₃NO₃
• 分子量: 324.591
• InChiKey: QAWBXAJZBBLQQN-UHFFFAOYSA-N

物化性质

• 沸点：
  341.0±52.0 °C(Predicted)
• 密度：
  1.458±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  41.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  L-缬氨酸甲酯 、 N-tert-butoxycarbonyl-3-(2,3,5-trichlorophenyl)oxaziridine 以 乙醚 为溶剂， 反应 24.0h， 生成 H-(N²-Boc)aVal-OMe
  参考文献：
  名称：

  N-Alkyloxycarbonyl-3-aryloxaziridines: Their Preparation, Structure, and Utilization As Electrophilic Amination Reagents

  摘要：

  AbstractThis paper reports the synthesis of a series of N‐protected oxaziridines (N‐Moc, Boc, Z or Fmoc) and discusses their ability to deliver their N‐alkoxycar‐bonyl fragment to amines, enolates, sulfur, and phosphorus nucleophiles (electrophilic amination). These oxaziridines are prepared by oxidation of the corresponding imines with oxone or anhydrous MCPBA lithium salt as the source of oxygen. They transfer their N‐protected fragment to primary and secondary amines to give protected hydrazines in fair to excellent yield. The nitrogen transfer to free amino acids (in form of their R4N+ salts) is particularly fast, even at low temperature, providing L (or D) N‐protected α‐hydrazino acids. Enolates are C‐aminated to give N‐protected α‐amino ketones, esters, or amides in modest yield, due to a side aldol reaction of the unreacted enolate with the released benzaldehyde. With tertiary amines (Et3N), sulfides (PhSMe), and phosphines (Ph3P), amination and oxidation proceed in a parallel way; the amount of amination product increases when the temperature is lowered (kinetic control). Some of the factors that can orient the oxaziridine reactivity towards amination or oxidation of nucleophiles are considered.

  DOI：

  10.1002/chem.19970031019
• 作为产物：
  描述：

  (4-氰基亚苄基)-氨基甲酸叔丁酯 在 LiMCPBA 作用下， 以 二氯甲烷 、 二氯甲烷-D2 、 甲苯 为溶剂， 反应 90.0h， 生成 N-tert-butoxycarbonyl-3-(2,3,5-trichlorophenyl)oxaziridine
  参考文献：
  名称：

  N-Alkyloxycarbonyl-3-aryloxaziridines: Their Preparation, Structure, and Utilization As Electrophilic Amination Reagents

  摘要：

  AbstractThis paper reports the synthesis of a series of N‐protected oxaziridines (N‐Moc, Boc, Z or Fmoc) and discusses their ability to deliver their N‐alkoxycar‐bonyl fragment to amines, enolates, sulfur, and phosphorus nucleophiles (electrophilic amination). These oxaziridines are prepared by oxidation of the corresponding imines with oxone or anhydrous MCPBA lithium salt as the source of oxygen. They transfer their N‐protected fragment to primary and secondary amines to give protected hydrazines in fair to excellent yield. The nitrogen transfer to free amino acids (in form of their R4N+ salts) is particularly fast, even at low temperature, providing L (or D) N‐protected α‐hydrazino acids. Enolates are C‐aminated to give N‐protected α‐amino ketones, esters, or amides in modest yield, due to a side aldol reaction of the unreacted enolate with the released benzaldehyde. With tertiary amines (Et3N), sulfides (PhSMe), and phosphines (Ph3P), amination and oxidation proceed in a parallel way; the amount of amination product increases when the temperature is lowered (kinetic control). Some of the factors that can orient the oxaziridine reactivity towards amination or oxidation of nucleophiles are considered.

  DOI：

  10.1002/chem.19970031019

文献信息

• Electrophilic amination reagents: A new method for the preparation of 3-Aryl-N-BOC (or N-FMOC) oxaziridines
  作者：Joe¨lle Vidal、Ste´phanie Damestoy、Andre´ Collet

  DOI：10.1016/0040-4039(95)00025-8

  日期：1995.2

  N-BOC or N-FMOC benzaldimines are oxidized to the corresponding 3-Aryl-N-BOC or N-FMOC oxaziridines by reaction with Li m-chloroperoxybenzoate under aprotic conditions. The new oxaziridines can transfer their N-BOC or N-FMOC group to morpholine to give the corresponding Nβ-protected hydrazines.

  通过在非质子条件下与间氯过氧苯甲酸锂反应，将N-BOC或N-FMOC苯甲二胺氧化为相应的3-芳基-N-BOC或N-FMOC恶唑烷。新的氧氮环丙烷可以在其N-BOC或N-FMOC基团转移到吗啉，得到相应的N β -保护的肼。