(1R,2S)-((E)-2-Propenyl)-cyclopropanecarboxylic acid ethyl ester

• 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: (1R,2S)-((E)-2-Propenyl)-cyclopropanecarboxylic acid ethyl ester
• 英文别名: ethyl (1R,2S)-2-[(E)-prop-1-enyl]cyclopropane-1-carboxylate
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: TXWMMLLWLONGEU-LFHXBRCSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S)-((E)-2-Propenyl)-cyclopropanecarboxylic acid ethyl ester 在 氢氧化钾 作用下， 以 水 为溶剂， 生成 trans-2-(E-1-propenyl)-cyclopropanecarboxylic acid
  参考文献：
  名称：

  重氮合成2-乙烯基环丙基的途径

  摘要：

  在室温下，由相应的亚硝基脲在甲醇中生成2-乙烯基环亚丙基（2），3-甲基-2-乙烯基环亚丙基（79,81）和2-（1-丙烯基）环亚丙基（95,97）。重氮途径通过不经历1，3-碳移位的2-乙烯基环丙烷重氮离子（例如43）的形成而引发。在重氮离子占优势的弱碱性甲醇中未发现环戊烯基产物。重氮离子的开环得到戊二烯基阳离子和由其衍生的产物。通过氘和甲基标记的分布证明了戊二烯基阳离子的离域化。在强碱存在下，1-重氮-2-乙烯基环丙烷（例如48）是由于重氮离子去质子化而产生的。独立产生潜在的产物4-重氮环戊烯（103）排除了48的重排。从103获得了大量的3-甲氧基环戊烯（108），但没有从48获得。由相应的重氮化合物中的氮损失引起的2-乙烯基环丙叉基2,79和95竞争性地经历了丙二烯形成和Skattebøl重排。C-2（81）或C-2'（97）处的顺式甲基可防止Skattebøl重排。环戊烯基3和83屈服4-

  DOI：

  10.1016/s0040-4020(01)96385-9
• 作为产物：
  描述：

  反-1,3-戊二烯 在 dirhodium tetraacetate sodium ethanolate 作用下， 反应 168.0h， 生成 (1R,2S)-((E)-2-Propenyl)-cyclopropanecarboxylic acid ethyl ester
  参考文献：
  名称：

  重氮合成2-乙烯基环丙基的途径

  摘要：

  在室温下，由相应的亚硝基脲在甲醇中生成2-乙烯基环亚丙基（2），3-甲基-2-乙烯基环亚丙基（79,81）和2-（1-丙烯基）环亚丙基（95,97）。重氮途径通过不经历1，3-碳移位的2-乙烯基环丙烷重氮离子（例如43）的形成而引发。在重氮离子占优势的弱碱性甲醇中未发现环戊烯基产物。重氮离子的开环得到戊二烯基阳离子和由其衍生的产物。通过氘和甲基标记的分布证明了戊二烯基阳离子的离域化。在强碱存在下，1-重氮-2-乙烯基环丙烷（例如48）是由于重氮离子去质子化而产生的。独立产生潜在的产物4-重氮环戊烯（103）排除了48的重排。从103获得了大量的3-甲氧基环戊烯（108），但没有从48获得。由相应的重氮化合物中的氮损失引起的2-乙烯基环丙叉基2,79和95竞争性地经历了丙二烯形成和Skattebøl重排。C-2（81）或C-2'（97）处的顺式甲基可防止Skattebøl重排。环戊烯基3和83屈服4-

  DOI：

  10.1016/s0040-4020(01)96385-9

文献信息

• Cyclopropanation of Alkenes, N–H and S–H Insertion of Ethyl Diazoacetate Catalysed by Ruthenium Porphyrin Complexes
  作者：Erwan Galardon、Paul Le Maux、Gérard Simonneaux

  DOI：10.1016/s0040-4020(99)01050-9

  日期：2000.1

  Isomeric distribution for the cyclopropanation of isoprene and 1,3-pentadiene with ethyl diazoacetate and competition studies of the cyclopropanation and diazo insertion into heteroatom–hydrogen bonds are also reported. All these results agree with a major electronic and steric influence on both the regiochemical and stereochemical control in the catalytic cyclopropanation and diazo insertion reactions

  报道了钌卟啉催化重氮乙酸乙酯与苯乙烯衍生物和α-杂原子烯烃的环丙烷化反应的产物收率，立体选择性和区域选择性，并将其与其他金属卟啉催化剂催化的环丙烷化反应的立体选择性进行了比较。当竞争环丙烷化速率或产物立体异构体比率与苯乙烯上各种环取代基团的Hammet常数作图时，观察到线性相关性。还报道了异戊二烯和1,3-戊二烯与重氮乙酸乙酯环丙烷化的同分异构分布，以及环丙烷化和重氮插入杂原子-氢键的竞争研究。
• Regio- and stereoselective cyclopropanation of functionalised dienes. Novel methodology for the synthesis of vinyl- and divinyl-cyclopropanes
  作者：István E. Markó、Thierry Giard、Shinichi Sumida、Anne-Elisabeth Gies

  DOI：10.1016/s0040-4039(02)00242-3

  日期：2002.3

  Dienes, bearing an electron-withdrawing substituent at C-1, are cyclopropanated regio- and stereo selectively at the C-C double bond proximal to this electron-withdrawing group. The highest selectivity is observed in the case of dienylboronates. The cyclopropanation of these substrates affords almost exclusively the synthetically useful 1-boronato-2-vinyl-cyclopropanes. (C) 2002 Elsevier Science Ltd. All rights reserved.
• 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.
• An Efficient and Highly Enantio- and Diastereoselective Cyclopropanation of Olefins Catalyzed by Schiff-Base Ruthenium(II) Complexes We thank the reviewers for their helpful comments. Support from the DuPont Company and the Beckman, Dreyfus, and Packard Foundations are gratefully acknowledged. S.T.N. is an Alfred P. Sloan Fellow.
  作者：Jason A. Miller、Wiechang Jin、SonBinh T. Nguyen

  DOI：10.1002/1521-3773(20020816)41:16<2953::aid-anie2953>3.0.co;2-2

  日期：2002.8.16
• DOYLE, M. P.;DOROW, R. L.;BUHRO, W. E.;GRIFFIN, J. H.;TAMBLYN, W. H.;TRUD+, ORGANOMETALLICS, 1984, 3, N 1, 44-52
  作者：DOYLE, M. P.、DOROW, R. L.、BUHRO, W. E.、GRIFFIN, J. H.、TAMBLYN, W. H.、TRUD+

  DOI：——

  日期：——