methyl (R)-(+)-1-phenylaziridine-2-carboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (R)-(+)-1-phenylaziridine-2-carboxylate
• 英文别名: methyl (2R)-1-phenylaziridine-2-carboxylate
• 化学式: C₁₀H₁₁NO₂
• 分子量: 177.203
• InChiKey: DDPHDRQDLJDMKX-BFHBGLAWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  29.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  N-phenyl-N-hydroxy-2,2-dimethylpropanamide 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 生成 methyl (R)-(+)-1-phenylaziridine-2-carboxylate
  参考文献：
  名称：

  Asymmetric synthesis of N-aryl aziridines

  摘要：

  The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (-)-8-phenylmenthol, (-)-quinine and (-)-Oppolzer's sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer's auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantio selection and a mechanism is proposed for the aziridination reaction. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00548-1

文献信息

• Enzymatic resolution of N-arylaziridine carboxylates
  作者：H.M. Sampath Kumar、M. Shesha Rao、P. Pawan Chakravarthy、J.S. Yadav

  DOI：10.1016/j.tetasy.2003.10.027

  日期：2004.1

  N-Arylaziridine-2-carboxylates have been enzymatically resolved using the lipase from Candida rugosa to afford optically active aziridine carboxylates in moderate to high enantiomeric purity. The absolute configuration of the unknown aziridine carboxylates was assigned as S by chemical correlation. (C) 2003 Elsevier Ltd. All rights reserved.
• Nitrile Biotransformations for the Efficient Synthesis of Highly Enantiopure 1-Arylaziridine-2-carboxylic Acid Derivatives and Their Stereoselective Ring-Opening Reactions
  作者：Jin-Yuan Wang、De-Xian Wang、Qi-Yu Zheng、Zhi-Tang Huang、Mei-Xiang Wang

  DOI：10.1021/jo062339v

  日期：2007.3.1

  Catalyzed by the Rhodococcus erythropolis AJ270 whole cell catalyst under very mild conditions, biotransformations of racemic 1-arylaziridine-2-carbonitriles proceeded efficiently and enantioselectively to produce highly enantiopure S-1-arylaziridine-2-carboxamides and R-1-arylaziridine-2-carboxylic acids in excellent yields. Although the nitrile hydratase exhibits no selectivity against all nitrile substrates, the amidase is highly R-enantioselective towards 1-arylaziridine-2-carboxamides. When treated with benzyl bromide, 1-phenylaziridine-2S-carboxamide underwent a highly regioselective and enantiospecific ring-opening reaction to afford an almost quantitative yield of R-beta-[(benzyl)phenylamino]-alpha-bromopropanamide (C-2 attack) and R-alpha-[(benzyl)phenylamino]-beta-bromopropanamide (C-3 attack) in a 10.5:1 ratio. Further treatment of the resulting ring-opening products with an N-nucleophilic reagent such as amine and azide led to, through most probably the aziridinium intermediate, the formation of S-alpha-substituted-beta-[(benzyl)phenylamino]propanamides in good chemical yields with high enantiomeric purity.
• Asymmetric synthesis of N-aryl aziridines
  作者：João Aires-de-Sousa、Sundaresan Prabhakar、Ana M. Lobo、Ana M. Rosa、Mário J.S. Gomes、Marta C. Corvo、David J. Williams、Andrew J.P. White

  DOI：10.1016/s0957-4166(01)00548-1

  日期：2002.1

  The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (-)-8-phenylmenthol, (-)-quinine and (-)-Oppolzer's sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer's auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantio selection and a mechanism is proposed for the aziridination reaction. (C) 2002 Elsevier Science Ltd. All rights reserved.