(4R,5S,2'R)-1,5-dimethyl-3-[(2'-aziridinyl)carbonyl]-4-phenylimidazolidin-2-one | 199122-48-0

• 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: (4R,5S,2'R)-1,5-dimethyl-3-[(2'-aziridinyl)carbonyl]-4-phenylimidazolidin-2-one
• 英文别名: (4S,5R)-1-[(2R)-aziridine-2-carbonyl]-3,4-dimethyl-5-phenylimidazolidin-2-one
• CAS: 199122-48-0
• 化学式: C₁₄H₁₇N₃O₂
• 分子量: 259.308
• InChiKey: IRMCJVAPZDRTPI-WCQGTBRESA-N

物化性质

• 沸点：
  397.7±52.0 °C(Predicted)
• 密度：
  1.246±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  62.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4R,5S,2'R)-1,5-dimethyl-3-[(2'-aziridinyl)carbonyl]-4-phenylimidazolidin-2-one 在 正丁基锂 、 N,N-二异丙基乙胺 、 copper(l) chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 (4R,5S)-1,5-dimethyl-4-phenyl-3-(2-propenoyl)-2-imidazolidinone
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure Aziridine-2-imides by Cyclization of Chiral 3‘-Benzyloxyamino Imide Enolates

  摘要：

  Aziridine-2-imides are prepared both in high yield and high diastereoselectivity from chiral 3'-benzyloxyamino imides 2, 3, and 8 by treatment with triethylamine in the presence of either TiCl4 or AlMe2Cl. 2 and 3 are easily obtained by a diastereoselective conjugate addition of O-benzylhydroxylamine promoted by Lewis acids to alpha,beta-unsaturated imides 1. The synthesis of 3'-(benzyloxyamino)propanoyl 8 is performed by addition to the acryloyl compound 6 of N-BOC O-benzylhydroxylamine followed by deprotection. The cyclization of 2 and 3 affords complete trans selectivity and yields up to 97% of the corresponding 3'-alkyl aziridines 4 and 5, while the cyclization of 8 affords a mixture of diasteroisomers 11, 12 in 86/14 ratio and a 95% yield. A mechanistic study has been made to rationalize the trans selectivity observed in the cyclization of 2 and 3. AM1 computations allow us to deduce that the reaction proceeds through cyclic titanium or aluminum enolate formation, and they reveal that enolates leading to trans aziridines are more stable than those leading to cis.

  DOI：

  10.1021/jo971254e
• 作为产物：
  描述：

  (4R,5S)-1,5-dimethyl-3-{3'-[(tert-butoxycarbonyl)(benzyloxy)amino]propanoyl}-4-phenylimidazolidin-2-one 在 盐酸 、 四氯化钛 、 三乙胺 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 1.0h， 生成 (4R,5S,2'R)-1,5-dimethyl-3-[(2'-aziridinyl)carbonyl]-4-phenylimidazolidin-2-one
  参考文献：
  名称：

  Synthesis of Enantiomerically Pure Aziridine-2-imides by Cyclization of Chiral 3‘-Benzyloxyamino Imide Enolates

  摘要：

  Aziridine-2-imides are prepared both in high yield and high diastereoselectivity from chiral 3'-benzyloxyamino imides 2, 3, and 8 by treatment with triethylamine in the presence of either TiCl4 or AlMe2Cl. 2 and 3 are easily obtained by a diastereoselective conjugate addition of O-benzylhydroxylamine promoted by Lewis acids to alpha,beta-unsaturated imides 1. The synthesis of 3'-(benzyloxyamino)propanoyl 8 is performed by addition to the acryloyl compound 6 of N-BOC O-benzylhydroxylamine followed by deprotection. The cyclization of 2 and 3 affords complete trans selectivity and yields up to 97% of the corresponding 3'-alkyl aziridines 4 and 5, while the cyclization of 8 affords a mixture of diasteroisomers 11, 12 in 86/14 ratio and a 95% yield. A mechanistic study has been made to rationalize the trans selectivity observed in the cyclization of 2 and 3. AM1 computations allow us to deduce that the reaction proceeds through cyclic titanium or aluminum enolate formation, and they reveal that enolates leading to trans aziridines are more stable than those leading to cis.

  DOI：

  10.1021/jo971254e

文献信息

• Dipeptides containing D-serine or D-isoserine from the same (R)-aziridine-2-imide by a simple reversal of the synthetic procedure
  作者：Giuliana Cardillo、Luca Gentilucci、Alessandra Tolomelli

  DOI：10.1016/s0040-4020(99)00989-8

  日期：1999.12

  The ring expansion of 3-unsubstituted (R)-aziridine-2-imide-containing dipeptide under acidic conditions gives rise to oxazoline-5-imide regio and stereoselectively, which can be hydrolysed to the dipeptide containing D-isoserine. On the other hand, the ring opening of 3-unsubstituted (R)-aziridine-2-ester dipeptide, easily obtained from the same (R)-aziridine, gives the regioisomeric dipeptide containing D-serine. (C) 1999 Elsevier Science Ltd. All rights reserved.