meso-8-(4-nitrobenzoyl)-8-azabicyclo[5.1.0]octane | 1138849-22-5

• 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: meso-8-(4-nitrobenzoyl)-8-azabicyclo[5.1.0]octane
• 英文别名: 8-(4-nitrobenzoyl)-8-azabicyclo[5.1.0]octane；[(1S,7R)-8-azabicyclo[5.1.0]octan-8-yl]-(4-nitrophenyl)methanone
• CAS: 1138849-22-5
• 化学式: C₁₄H₁₆N₂O₃
• 分子量: 260.293
• InChiKey: QNDOYACZFDOZEB-NNQSOWQGSA-N

物化性质

• 沸点：
  449.3±28.0 °C(predicted)
• 密度：
  1.283±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  65.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  meso-8-(4-nitrobenzoyl)-8-azabicyclo[5.1.0]octane 在 叠氮基三甲基硅烷 、 C₈₂H₇₈N₆O₁₀Y₂ 作用下， 以 1,2-二氯乙烷 为溶剂， 以47%的产率得到(1R,2R)-1-azido-2-[N-(4-nitrobenzoyl)amino]cycloheptane
  参考文献：
  名称：

  离散钇配合物催化TMSN3或TMMSCN介导的氮杂氮丙啶的对映选择性脱对称

  摘要：

  是这样吗 钇-salen二聚体（见结构； N蓝色，O红色，Y品红色）通过TMSCN和TMSN 3催化内消旋氮丙啶的高度对映选择性开环。为了解释单聚体催化剂和二聚体催化剂之间选择性的巨大差异，提出了一种基于二聚体固态结构的双金属机理。

  DOI：

  10.1002/anie.200804415
• 作为产物：
  描述：

  (1R,7S)-8-azabicyclo[5.1.0]octane 、 4-硝基苯甲酰氯 在 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 meso-8-(4-nitrobenzoyl)-8-azabicyclo[5.1.0]octane
  参考文献：
  名称：

  离散钇配合物催化TMSN3或TMMSCN介导的氮杂氮丙啶的对映选择性脱对称

  摘要：

  是这样吗 钇-salen二聚体（见结构； N蓝色，O红色，Y品红色）通过TMSCN和TMSN 3催化内消旋氮丙啶的高度对映选择性开环。为了解释单聚体催化剂和二聚体催化剂之间选择性的巨大差异，提出了一种基于二聚体固态结构的双金属机理。

  DOI：

  10.1002/anie.200804415

文献信息

• Toward a rational design of the assembly structure of polymetallic asymmetric catalysts: design, synthesis, and evaluation of new chiral ligands for catalytic asymmetric cyanation reactions
  作者：Ikuo Fujimori、Tsuyoshi Mita、Keisuke Maki、Motoo Shiro、Akihiro Sato、Sanae Furusho、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1016/j.tet.2007.02.081

  日期：2007.6

  New chiral ligands (4 and 5) for polymetallic asymmetric catalysts were designed based on the hypothesis that the assembled structure should be stable when made from a stable module 8. A metal-ligand 5:6+mu-oxo+OH complex was generated from Gd((OPr)-Pr-i)(3) and 4 or 5, and this complex was an improved asymmetric catalyst for the desymmetrization of meso-aziridines with TMSCN and conjugate addition of TMSCN to alpha,beta-unsaturated N-acylpyrroles, compared to the previously reported catalysts derived from 1-3. These two groups of catalysts produced opposing enantioselectivity even though the ligands had the same chirality. The functional difference in the asymmetric catalysts is derived from differences in the higher-order structure of the polymetallic catalysts. (C) 2007 Elsevier Ltd. All rights reserved.
• Catalytic Enantioselective Desymmetrization of <i>meso</i>-<i>N</i>-Acylaziridines with TMSCN
  作者：Tsuyoshi Mita、Ikuo Fujimori、Reiko Wada、Jianfeng Wen、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1021/ja053486y

  日期：2005.8.1

  A catalytic enantioselective desymmetrization of meso-N-p-nitrobenzoylaziridines with TMSCN was developed using a chiral gadolinium catalyst generated from Gd(OiPr)3 and d-glucose-derived ligand 1. In this reaction, the addition of a catalytic amount of trifluoroacetic acid (TFA) improved enantioselectivity. High enantioselectivity was obtained from a range of meso-aziridines at 0-60 degrees C. The product could be easily transformed into beta-amino acids. Thus, the developed catalytic enantioselective desymmetrization reaction allowed for efficient catalytic synthesis of chiral cyclic beta-amino acids. The incorporation of TFA into the catalyst complex was observed using ESI-MS. Generation of this new complex might be the origin of the improved enantioselectivity.