6-(3,5-dinitrobenzoyl)-6-azabicyclo[3.1.0]hexane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 6-(3,5-dinitrobenzoyl)-6-azabicyclo[3.1.0]hexane
• 英文别名: N-(3,5-dinitrobenzoyl)-6-azabicyclo[3.1.0]hexane；[(1S,5R)-6-azabicyclo[3.1.0]hexan-6-yl]-(3,5-dinitrophenyl)methanone
• 化学式: C₁₂H₁₁N₃O₅
• 分子量: 277.236
• InChiKey: CBJLBMBVEWORTH-QYJAPNMZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  112
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6-(3,5-dinitrobenzoyl)-6-azabicyclo[3.1.0]hexane 、 苯硒酚 在 (R)-VAPOL 、 三甲基苯基硒硅烷 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以90%的产率得到(1R,2R)-1-phenylseleno-2-[N-(3,5-dinitrobenzoyl)amino]cyclopentane
  参考文献：
  名称：

  A general phosphoric acid-catalyzed desymmetrization of meso-aziridines with silylated selenium nucleophiles

  摘要：

  首次报道了硒亲核试剂参与的中位氮杂环丙烷去对称化反应。该反应以VAPOL磷酸氢二钠为促进剂，采用（苯硒基）三甲基硅烷作为亲核试剂，其适用范围非常广泛，且具有高度的对映选择性（84-99% 对映体过量）。

  DOI：

  10.1039/c1ob05837a
• 作为产物：
  描述：

  3,5-二硝基苯甲酸 在 N,N'-二环己基碳二亚胺 作用下， 以 1,4-二氧六环 、 乙二醇二甲醚 为溶剂， 反应 15.0h， 生成 6-(3,5-dinitrobenzoyl)-6-azabicyclo[3.1.0]hexane
  参考文献：
  名称：

  Scalable Synthesis of N-Acylaziridines from N-Tosylaziridines

  摘要：

  N-Acylaziridines are important starting materials for the synthesis of chiral amine derivatives. The traditional methods for producing these activated aziridines have significant drawbacks. The gram scale synthesis of N-acylaziridines by deprotection of N-tosylaztridines and reprotection with N-hydroxysuccinimide derivatives is described. Mono- and disubstituted aziridines perform well, with complete retention of stereochemical purity. The consistently moderate yields are linked to the N-tosylaziridine deprotection step, while acylation with N-hydroxysuccinimide derivatives is highly efficient.

  DOI：

  10.1021/jo401267j

文献信息

• Catalytic Enantioselective Ring-Opening Reaction of<i>meso</i>-Aziridines with α-Isothiocyanato Imides
  作者：Yi-Ming Cao、Fu-Ting Zhang、Fang-Fang Shen、Rui Wang

  DOI：10.1002/chem.201300297

  日期：2013.7.15

  Open up your chemistry! By using cinchonine‐based trimeric quaternary ammonium salts as catalysts, meso‐aziridines can be ring‐opened, in an enantioselective manner, through nucleophilic addition of the sulfur atom of α‐isothiocyanato imides (see scheme; PG=protecting group). This synthetic method provides an efficient way to access useful chiral β‐aminothiooxazole compounds.

  打开你的化学！通过使用基于辛可宁的三聚体季铵盐作为催化剂，可以通过亲核加成α-异硫氰酸根酰亚胺的硫原子，以对映选择性的方式将内消旋氮丙啶开环（参见方案; PG =保护基）。这种合成方法提供了一种有效的途径来获得有用的手性β-氨基硫恶唑化合物。
• De Novo Synthesis of Tamiflu via a Catalytic Asymmetric Ring-Opening of <i>meso</i>-Aziridines with TMSN₃
  作者：Yuhei Fukuta、Tsuyoshi Mita、Nobuhisa Fukuda、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1021/ja061696k

  日期：2006.5.1

  An asymmetric ring-opening reaction of meso-aziridines with TMSN3 was developed using a catalyst prepared from Y(OiPr)3 and chiral ligand 2 in a 1:2 ratio. Excellent enantioselectivity was realized from a wide range of substrates with a practical catalyst loading. The products were efficiently converted to enantiomerically enriched 1,2-diamines, which are versatile chiral building blocks for pharmaceuticals and chiral ligands. This reaction was applied to a catalytic asymmetric synthesis of Tamiflu, a very important anti-influenza drug containing a chiral 1,2-diamino functionality.
• Catalytic Asymmetric Ring-Opening of<i>meso-</i>Aziridines with Malonates under Heterodinuclear Rare Earth Metal Schiff Base Catalysis
  作者：Yingjie Xu、Luqing Lin、Motomu Kanai、Shigeki Matsunaga、Masakatsu Shibasaki

  DOI：10.1021/ja201492x

  日期：2011.4.20

  Catalytic asymmetric ring-opening of meso-aziridines with malonates is described. The combined use of two rare earth metal sources with different properties promoted the desired ring-opening reaction. A 1:1:1 mixture of a heterobimetallic La(O-iPr)(3)/Yb(OTf)(3)/Schiff base la (0.25-10 mol %) efficiently promoted the reaction of five-, six-, and seven-membered ring cyclic meso-aziridines as well as acyclic meso-aziridines with dimethyl, diethyl, and dibenzyl malonates, giving chiral cyclic and acyclic gamma-amino esters in 99-63% yield and > 99.5-97% ee.
• Highly Enantioselective Synthesis of β-Amidophenylthioethers by Organocatalytic Desymmetrization of <i>meso</i>-Aziridines
  作者：Giorgio Della Sala、Alessandra Lattanzi

  DOI：10.1021/ol901209n

  日期：2009.8.6

  The desymmetrization of N-acylaziridines with Me3SiSPh, catalyzed by commercially available (R) and (S)-VAPOL hydrogen phosphate, produced beta-(N-acylamino)phenylthioethers in a highly enantioselective and efficient manner (78-99% ee). The selection of the suitable aziridine/nucleophile/catalyst molar ratio is crucial to obtain high ee's.
• Catalytic Enantioselective Desymmetrization of meso-Aziridines with Fluoromalonates
  作者：Shigeki Matsunaga、Seiya Fukagawa、Yingjie Xu、Masahiro Anada、Tatsuhiko Yoshino

  DOI：10.3987/com-17-13725

  日期：——

  Catalytic enantioselective desymmetrization of meso-aziridines with fluoromalonates is described. Optimization studies revealed that the appropriate combination of Bronsted basic metal and Lewis acidic metal is important for promoting the reaction using fluoromalonates. A heterodinuclear Gd(OiPr)(3)/Y(OTf)(3)/Schiff base = 1:1:1 was the best catalyst, and ring-opening adducts, synthetic precursors for alpha-fluoro-gamma-amino acids, were obtained in 98%similar to 17% yield and >99.5%similar to 99% ee. Transformation of the ring-opening adduct into alpha-fluoro-gamma-lactam was also demonstrated.