(4R,5S)-1,5-dimethyl-4-phenyl-3-[(2R,3S)-3-propylaziridine-2-carbonyl]imidazolidin-2-one | 176792-03-3

• 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)-1,5-dimethyl-4-phenyl-3-[(2R,3S)-3-propylaziridine-2-carbonyl]imidazolidin-2-one
• CAS: 176792-03-3
• 化学式: C₁₇H₂₃N₃O₂
• 分子量: 301.389
• InChiKey: PXJXZDGESJFFLD-MHEUCROKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 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)-1,5-dimethyl-4-phenyl-3-[(2R,3S)-3-propylaziridine-2-carbonyl]imidazolidin-2-one 在 吡啶 、 4-二甲氨基吡啶 、 正丁基锂 、 氨 、 甲基氯化镁 、 silica gel 作用下， 以 二氯甲烷 、 氯仿 、 二甲基亚砜 为溶剂， 反应 79.17h， 生成 (4R,5S,2'R,3'S)-1,5-dimethyl-3-(2'-acetamido-3'-acetoxybutyryl)-4-phenylimidazolidin-2-one
  参考文献：
  名称：

  非对映选择性加布里埃尔-克罗姆韦尔反应合成对映体纯的反式氮丙啶-2-羧酸酯

  摘要：

  通过将氨共轭添加到α，β-不饱和手性酰亚胺中，然后用苄氧基锂处理，可以高产率和选择性地获得苄基氮丙啶-2-羧酸苄酯。氮丙啶环扩展成恶唑啉可以确定新形成的立体异构中心的绝对立体化学。

  DOI：

  10.1016/0957-4166(96)00071-7
• 作为产物：
  描述：

  (4S,5R)-1-[(E)-hex-2-enoyl]-3,4-dimethyl-5-phenylimidazolidin-2-one 在 二甲基氯化铝 、 四氯化钛 、 三乙胺 作用下， 反应 0.75h， 生成 (4R,5S)-1,5-dimethyl-4-phenyl-3-[(2R,3S)-3-propylaziridine-2-carbonyl]imidazolidin-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

• Ring expansion of N-acyl aziridine-2-imides to oxazoline-4-imides, useful precursors of pure β-Hydroxy α-aminoacids
  作者：Giuliana Cardillo、Luca Gentilucci、Alessandra Tolomelli、Claudia Tomasini

  DOI：10.1016/s0040-4039(97)01630-4

  日期：1997.9

  Optically active N-acyl aziridine 2-imides or 2-carboxylates rearrange to oxazoline-4-imides or 4-carboxylates with high regio and stereo control. This ring expansion followed by mild hydrolisis allows the synthesis of enantiomerically pure β-hydroxy α-aminoacid precursors.

  光学活性的N-酰基氮丙啶2​​-酰亚胺或2-羧酸酯在高区域和立体控制下重排为oxazoline-4-酰亚胺或4-羧酸酯。该扩环随后温和的水解允许合成对映体纯的β-羟基α-氨基酸前体。
• Cardillo, Giuliana; Casolari, Sonia; Gentilucci, Luca, Angewandte Chemie, 1996, vol. 108, # 16, p. 1939 - 1941
  作者：Cardillo, Giuliana、Casolari, Sonia、Gentilucci, Luca、Tomasini, Claudia

  DOI：——

  日期：——
• Synthesis of Enantiomerically Pure Aziridine-2-imides by Cyclization of Chiral 3‘-Benzyloxyamino Imide Enolates
  作者：Alessandro Bongini、Giuliana Cardillo、Luca Gentilucci、Claudia Tomasini

  DOI：10.1021/jo971254e

  日期：1997.12.1

  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.
• Synthesis of enantiomerically pure trans aziridine-2-carboxylates by diastereoselective Gabriel-cromwell reaction
  作者：Giuliana Cardillo、Luca Gentilucci、Claudia Tomasini、Maria Pilar Visa Castejon-Bordas

  DOI：10.1016/0957-4166(96)00071-7

  日期：1996.3

  Benzyl aziridine-2-carboxylates have been obtained in high yield and selectivity by conjugate addition of ammonia to α,β-unsaturated chiral imides followed by treatment with lithium benzyloxide. A ring-expansion of the aziridine to an oxazoline allowed the determination of the absolute stereochemistry for the newly formed stereogenic centres.

  通过将氨共轭添加到α，β-不饱和手性酰亚胺中，然后用苄氧基锂处理，可以高产率和选择性地获得苄基氮丙啶-2-羧酸苄酯。氮丙啶环扩展成恶唑啉可以确定新形成的立体异构中心的绝对立体化学。