cis-1-benzhydryl-(3S)-(4-nitrophenyl)-aziridine-(2S)-carboxylic acid ethyl ester | 382142-90-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-1-benzhydryl-(3S)-(4-nitrophenyl)-aziridine-(2S)-carboxylic acid ethyl ester
• 英文别名: (2S,3S)-ethyl 1-benzhydryl-3-(4-nitrophenyl)aziridine-2-carboxylate；ethyl (2S,3S)-1-benzhydryl-3-(4-nitrophenyl)aziridine-2-carboxylate
• CAS: 382142-90-7
• 化学式: C₂₄H₂₂N₂O₄
• 分子量: 402.45
• InChiKey: BCWMCWDSOSLQFX-REQUTJCGSA-N

物化性质

• 熔点：
  139-140 °C(Solv: ethyl acetate (141-78-6); hexane (110-54-3))
• 沸点：
  517.9±50.0 °C(Predicted)
• 密度：
  1.271±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  75.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  cis-1-benzhydryl-(3S)-(4-nitrophenyl)-aziridine-(2S)-carboxylic acid ethyl ester 在 sodium tetrahydroborate 作用下， 以 甲醇 、 1,2-二氯乙烷 为溶剂， 反应 1.5h， 生成 氯霉素
  参考文献：
  名称：

  An Efficient Synthesis of (−)-Chloramphenicol via Asymmetric Catalytic Aziridination:  A Comparison of Catalysts Prepared from Triphenylborate and Various Linear and Vaulted Biaryls

  摘要：

  [GRAPHICS]The antibiotic (-)-choramphenicol has been synthesized in only four steps from p-nitro-benzaldehyde in optically pure form from an asymmetric catalytic aziridination reaction with a chiral catalyst prepared from triphenylborate and the (R)-VAPOL ligand. Catalysts generated from the VAPOL and VANOL ligands give much higher asymmetric induction than do catalysts prepared from 6,6'-diphenylVAPOL, BINOL, and BANOL ligands.

  DOI：

  10.1021/ol010180x
• 作为产物：
  描述：

  二苯甲胺 在 三苯基硼酸酯 、 magnesium sulfate 、 2R)-(+)-3,3'-二苯基-[2,2'-联二萘]-1,1'-二醇 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 36.0h， 生成 cis-1-benzhydryl-(3S)-(4-nitrophenyl)-aziridine-(2S)-carboxylic acid ethyl ester
  参考文献：
  名称：

  An Efficient Synthesis of (−)-Chloramphenicol via Asymmetric Catalytic Aziridination:  A Comparison of Catalysts Prepared from Triphenylborate and Various Linear and Vaulted Biaryls

  摘要：

  [GRAPHICS]The antibiotic (-)-choramphenicol has been synthesized in only four steps from p-nitro-benzaldehyde in optically pure form from an asymmetric catalytic aziridination reaction with a chiral catalyst prepared from triphenylborate and the (R)-VAPOL ligand. Catalysts generated from the VAPOL and VANOL ligands give much higher asymmetric induction than do catalysts prepared from 6,6'-diphenylVAPOL, BINOL, and BANOL ligands.

  DOI：

  10.1021/ol010180x

文献信息

• Catalytic Asymmetric Aziridination of Benzhydryl Imines and Diazoacetate­ Esters with BOROX Catalysts from 3,3′-Disubstituted VANOL Ligands
  作者：William D. Wulff、Yong Guan、Zhenjie Lu、Xiaopeng Yin、Aliakbar Mohammadlou、Richard J. Staples

  DOI：10.1055/s-0039-1690860

  日期：2020.7

  into boroxinate catalysts that were used to screen the catalytic asymmetric aziridination of benzhydryl imines with ethyl diazoacetate. Each catalyst was screened in the reaction of imines generated from benzaldehyde and cyclohexanecarboxaldehyde and some with 4-nitro- and 4-methoxybenzaldehyde. In addition, the first report of the effect of the ester substituent of the diazoacetate ester on the asymmetric

  这项工作详述了22种新的手性VANOL配体的合成，这些配体在配体的3和3'位上的取代基性质不同。将这些配体掺入硼氧杂环丁烷酸酯催化剂中，该催化剂用于筛选重氮基乙酸乙酯与苯甲基亚胺的催化不对称叠氮化。在由苯甲醛和环己烷甲醛以及一些与4-硝基-和4-甲氧基苯甲醛生成的亚胺的反应中，对每种催化剂进行了筛选。此外，首次报道了重氮乙酸酯的酯取代基对这些叠氮化反应中不对称诱导的影响。还报道了由VANOL衍生的配体产生的硼氧杂环丁酸酯催化剂的第一X射线结构。
• Catalytic Asymmetric Aziridination with Borate Catalysts Derived from VANOL and VAPOL Ligands: Scope and Mechanistic Studies
  作者：Yu Zhang、Aman Desai、Zhenjie Lu、Gang Hu、Zhensheng Ding、William D. Wulff

  DOI：10.1002/chem.200701558

  日期：2008.4.18

  An extended study of the scope and mechanism of the catalytic asymmetric aziridination of imines with ethyl diazoacetate mediated by catalysts prepared from the VANOL and VAPOL ligands and triphenylborate is described. Nonlinear studies with scalemic VANOL and VAPOL reveal an essentially linear relationship between the optical purity of the ligand and the product suggesting that the catalyst incorporates

  描述了由VANOL和VAPOL配体以及硼酸三苯酯制备的催化剂介导的亚胺与重氮乙酸乙酯催化不对称叠氮化的范围和机理的扩展研究。用鳞状VANOL和VAPOL进行的非线性研究表明，配体和产物的光学纯度之间存在基本线性的关系，这表明催化剂掺入了单个配体分子。由（1）H NMR研究表明，由B（OPh）（3）制备的催化剂中存在两种物质，或者是VANOL或VAPOL。催化剂混合物的质谱分析表明，一种物质涉及一个配体分子和一个硼原子（B1），另一种物质涉及一个配体和两个硼原子（B2）。后者可以配制成线性或环状焦硼酸盐，（11）B NMR谱图与线性焦硼酸盐结构最一致。已开发出几种用于催化剂制备的新方案，其允许生成比例为10：1至1:20的B1和B2催化剂的混合物。对富含B1和B2物种的催化剂的研究表明，B2催化剂是VAPOL催化的不对称叠氮化反应中的活性催化剂，比B1催化剂具有更高的不对称诱导率和速率。差异
• Catalytic Asymmetric Aziridination with a Chiral VAPOL−Boron Lewis Acid
  作者：Jon C. Antilla、William D. Wulff

  DOI：10.1021/ja9905187

  日期：1999.6.1
• An Efficient Synthesis of (−)-Chloramphenicol via Asymmetric Catalytic Aziridination:  A Comparison of Catalysts Prepared from Triphenylborate and Various Linear and Vaulted Biaryls
  作者：Catherine Loncaric、William D. Wulff

  DOI：10.1021/ol010180x

  日期：2001.11.1

  [GRAPHICS]The antibiotic (-)-choramphenicol has been synthesized in only four steps from p-nitro-benzaldehyde in optically pure form from an asymmetric catalytic aziridination reaction with a chiral catalyst prepared from triphenylborate and the (R)-VAPOL ligand. Catalysts generated from the VAPOL and VANOL ligands give much higher asymmetric induction than do catalysts prepared from 6,6'-diphenylVAPOL, BINOL, and BANOL ligands.