2-methylcyclopropane-1,1-dicarboxylic acid | 890004-07-6

• 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: 2-methylcyclopropane-1,1-dicarboxylic acid
• 英文别名: (2R)-2-methylcyclopropane-1,1-dicarboxylic acid
• CAS: 890004-07-6
• 化学式: C₆H₈O₄
• 分子量: 144.127
• InChiKey: SPAYAPLBTKGPME-GSVOUGTGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-methylcyclopropane-1,1-dicarboxylic acid 、 三甲基硅烷化重氮甲烷 在 甲醇 作用下， 以 乙醚 、 苯 为溶剂， 反应 5.0h， 以150 mg的产率得到(-)-(2R)-2-methylcyclopropane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Enantioselective, Facially Selective Carbomagnesation of Cyclopropenes

  摘要：

  Described is the facially selective and enantioselective addition of carbon nucleophiles to prochiral 3-hydroxymethylcyclopropenes. The process creates up to four stereocenters in a tandem addition/capture sequence that combines three simple materials to give complex and diverse products. The asymmetry is induced by the inexpensive and recoverable ligand (S)-N-methylprolinol. The enantioselectivity (90-98% ee with MeMgCl) is high for a range of cyclopropenes and electrophiles. Importantly, the diastereoselectivity is complementary to that obtained by enantioselective cyclopropanation with aryldiazoacetates. High enantioselectivities are obtained only when methoxide is included in the reaction. Evidence is provided that at least two chiral ligands are involved in the enantioselectivity-determining step.

  DOI：

  10.1021/ja058101q
• 作为产物：
  描述：

  (2-methyl-1-phenyl-cycloprop-1-yl)methanol 在 ruthenium trichloride 、 sodium periodate 作用下， 以 四氯化碳 、 水 、 乙腈 为溶剂， 反应 24.0h， 生成 2-methylcyclopropane-1,1-dicarboxylic acid
  参考文献：
  名称：

  Enantioselective, Facially Selective Carbomagnesation of Cyclopropenes

  摘要：

  Described is the facially selective and enantioselective addition of carbon nucleophiles to prochiral 3-hydroxymethylcyclopropenes. The process creates up to four stereocenters in a tandem addition/capture sequence that combines three simple materials to give complex and diverse products. The asymmetry is induced by the inexpensive and recoverable ligand (S)-N-methylprolinol. The enantioselectivity (90-98% ee with MeMgCl) is high for a range of cyclopropenes and electrophiles. Importantly, the diastereoselectivity is complementary to that obtained by enantioselective cyclopropanation with aryldiazoacetates. High enantioselectivities are obtained only when methoxide is included in the reaction. Evidence is provided that at least two chiral ligands are involved in the enantioselectivity-determining step.

  DOI：

  10.1021/ja058101q

文献信息

• Total Synthesis of (+)-Frondosin A. Application of the Ru-Catalyzed [5+2] Cycloaddition
  作者：Barry M. Trost、Yimin Hu、Daniel B. Horne

  DOI：10.1021/ja073272b

  日期：2007.9.1

  The first total synthesis of (+)-frondosin A was accomplished in 19 longest linear and 21 total steps from commercially available materials. The key features of the synthesis include a Ru-catalyzed [5+2] cycloaddition, a Claisen rearrangement, and a ring expansion to construct the core of the frondosin A in a diastereoselective and regioselective fashion. This is the first application of a Ru-catalyzed [5+2] cycloaddition in the total synthesis of a natural product. Through this synthesis, the absolute configuration of (+)-frondosin A was established.
• Enantioselective, Facially Selective Carbomagnesation of Cyclopropenes
  作者：Xiaozhong Liu、Joseph M. Fox

  DOI：10.1021/ja058101q

  日期：2006.5.1

  Described is the facially selective and enantioselective addition of carbon nucleophiles to prochiral 3-hydroxymethylcyclopropenes. The process creates up to four stereocenters in a tandem addition/capture sequence that combines three simple materials to give complex and diverse products. The asymmetry is induced by the inexpensive and recoverable ligand (S)-N-methylprolinol. The enantioselectivity (90-98% ee with MeMgCl) is high for a range of cyclopropenes and electrophiles. Importantly, the diastereoselectivity is complementary to that obtained by enantioselective cyclopropanation with aryldiazoacetates. High enantioselectivities are obtained only when methoxide is included in the reaction. Evidence is provided that at least two chiral ligands are involved in the enantioselectivity-determining step.