ethyl (1S,2S)-2-ethoxycyclopropane-1-carboxylate | 5604-58-0

• 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: ethyl (1S,2S)-2-ethoxycyclopropane-1-carboxylate
• CAS: 5604-58-0；60212-44-4；71666-09-6；141269-61-6；141269-62-7
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: KIIOJVVKDDBEBK-BQBZGAKWSA-N

物化性质

• 沸点：
  82 °C
• 密度：
  0.994 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  乙烯基乙醚 、 重氮乙酸乙酯 在 Zn₄O{Ru(L)(Py)2Cl} 作用下， 以 二氯甲烷 为溶剂， 生成 ethyl trans-2-ethoxycyclopropanecarboxylate 、 ethyl (1S,2S)-2-ethoxycyclopropane-1-carboxylate
  参考文献：
  名称：

  Chiral metal–organic frameworks with tunable open channels as single-site asymmetric cyclopropanation catalysts

  摘要：

  一对具有相同催化位点但开放通道尺寸不同的互穿和非互穿手性金属有机框架催化了取代的末端烯烃的不对称环丙烷化反应，具有极佳的非对映选择性（高达 9.6）和对映选择性（高达 >99%）。

  DOI：

  10.1039/c2cc32232c

文献信息

• Actuation of Asymmetric Cyclopropanation Catalysts: Reversible Single-Crystal to Single-Crystal Reduction of Metal-Organic Frameworks
  作者：Joseph M. Falkowski、Cheng Wang、Sophie Liu、Wenbin Lin

  DOI：10.1002/anie.201104086

  日期：2011.9.5

  To and fro: Chiral metal–organic frameworks (CMOFs) derived from redox‐active ruthenium/salen building blocks exhibited reversible single‐crystal to single‐crystal reduction and reoxidation. The catalytically inactive RuIII CMOFs (green; see picture) were reduced to RuII CMOFs (red) that were highly active for the asymmetric cyclopropanation of alkenes with very high diastereo‐ and enantioselectivities

  来回：从具有氧化还原活性的钌/ salen结构单元衍生的手性金属有机骨架（CMOF）表现出可逆的单晶至单晶还原和再氧化作用。具有催化活性的Ru III CMOF（绿色；参见图片）被还原为Ru II CMOF（红色），对非对映和对映选择性很高的烯烃的不对称环丙烷化反应具有很高的活性。
• Recyclable Polymer- and Silica-Supported Ruthenium(II)-Salen Bis-pyridine Catalysts for the Asymmetric Cyclopropanation of Olefins
  作者：Christopher S. Gill、Krishnan Venkatasubbaiah、Christopher W. Jones

  DOI：10.1002/adsc.200800779

  日期：2009.6

  Abstractmagnified imageHomogeneous ruthenium(II)‐salen bis‐pyridine complexes are known to be highly active and selective catalysts for the asymmetric cyclopropanation of terminal olefins. Here, new methods of heterogenization of these Ru‐salen catalysts on polymer and porous silica supports are demonstrated for the facile recovery and recycle of these expensive catalysts. Activities, selectivities, and recyclabilities are investigated and compared to the analogous homogeneous and other supported catalysts for asymmetric cyclopropanation reactions. The catalysts are characterized with a variety of methods including solid state cross‐polarization magic‐angle spinning (CP MAS) 13C and 29Si NMR, FT‐IR, elemental analysis, and thermogravimetric analysis. Initial investigations produced catalysts possessing high selectivities but decreasing activities upon reuse. Addition of excess pyridine during the washing steps between cycles was observed to maintain high catalytic activities over multiple cycles with no impact on selectivity. Polymer‐supported catalysts showed superior activity and selectivity compared to the porous silica‐supported catalyst. Additionally, a longer, flexible linker between the Ru‐salen catalyst and support was observed to increase enantioselectivity and diastereoselectivity, but had no effect on activity of the resin catalysts. Furthermore, the polymer‐supported Ru‐salen‐Py2 catalysts were found to generate superior selectivities and yields compared to other leading heterogeneous asymmetric cyclopropanation catalysts.