methyl N-(p-methylphenyl)aziridine-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 N-(p-methylphenyl)aziridine-2-carboxylate
• 英文别名: (R)-methyl 1-(p-tolyl)aziridine-2-carboxylate；methyl (R)-(+)-1-p-tolylaziridine-2-carboxylate；methyl (2R)-1-(4-methylphenyl)aziridine-2-carboxylate
• 化学式: C₁₁H₁₃NO₂
• 分子量: 191.23
• InChiKey: AZNTXKGFOXQQSW-RWANSRKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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-羟基-N-(4-甲基苯基)苯甲酰胺 、 丙烯酸甲酯（MA） 在 sodium hydroxide 、 9-O-[p-Ts-N-(3-CHO-5-Me-2-OH-C₆H₂-CH₂)]-cinchonidinium*Cl(-) 作用下， 以 甲苯 为溶剂， 反应 2.0h， 生成 methyl N-(p-methylphenyl)aziridine-2-carboxylate 、 methyl N-(p-methylphenyl)aziridine-2-carboxylate
  参考文献：
  名称：

  Synthesis of AsymmetricN-Arylaziridine Derivatives Using a New Chiral Phase-Transfer Catalyst

  摘要：

  利用从金鸡纳生物碱中提取的手性相转移催化剂（CPTCs），以对映体选择性方式从 N-酰基-N-芳基羟胺和缺电子烯烃合成了取代的 N-芳基氮丙啶衍生物。通过各种光谱技术（如傅立叶变换红外光谱、1H NMR、13C NMR 和质谱）以及元素分析，确定了 CPTC 的结构。研究了一系列 CPTC 在产率和ee方面的效率和手性。化学收率在 24-92% 之间，ee 为 29-95%。据观察，在以辛可尼丁为催化剂的情况下，S-对映体比 R-对映体更占优势；而在以辛可尼丁为催化剂的 CPTC 情况下，R-对映体更占优势。我们在此提出了形成手性氮丙啶的合适机制以及一系列 N-芳基氮丙啶衍生物的优化程序。

  DOI：

  10.1055/s-2005-869976

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.