(1S*,2R*,3R*)-ethyl 2-ethyl-3-methylcyclopropanecarboxylate

• 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: (1S*,2R*,3R*)-ethyl 2-ethyl-3-methylcyclopropanecarboxylate
• 英文别名: ethyl (1R,2S,3S)-2-ethyl-3-methylcyclopropane-1-carboxylate
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: WFWFEFCJHGQIQA-BIIVOSGPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  反-2-戊烯 、 diphenylsulfonium 2-ethoxy-2-oxoethylide 在 dirhodium tetraacetate 重氮乙酸乙酯 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 20.0h， 生成 (1R,2R,3R)-ethyl 2-ethyl-3-methylcyclopropanecarboxylate 、 (1S*,2R*,3R*)-ethyl 2-ethyl-3-methylcyclopropanecarboxylate
  参考文献：
  名称：

  Transition-Metal-Catalyzed Carbenoid Reactions of Sulfonium Ylides

  摘要：

  Olefins undergo cyclopropanation with diphenylsulfonium (ethoxycarbonyl)methylide (= diphenylsulfonium 2-ethoxy-2-oxoethylide; 3a) in the presence of chiral Cu-I or Rh-II catalysts, trans/cis Ratios and ee's of the cyclopropanes 6 obtained with this ylide in the presence of a chiral Cu-I catalyst 7 are identical with those obtained with ethyl diazoacetate (4). In the case of catalysis with Rh-II, the trans/cis ratios of the cyclopropanes as well as the enantioselectivity change slightly upon going from the ylide 3a to diazoacetate 4.

  DOI：

  10.1002/(sici)1522-2675(19990609)82:6<935::aid-hlca935>3.0.co;2-x

文献信息

• Complexation of a Singlet Carbene by a Fluoroalkane. Modification of 1:CHCO2Et Selectivity in Perfluorohexane Solution and ab Initio Calculations
  作者：Judith M. Swanson、Curt A. Dvorak、JoAnn P. DeLuca、Jean M. Standard

  DOI：10.1021/jo00090a020

  日期：1994.6

  We have compared product distributions from reactions of (1):CH2 with 2,5-dimethylhexane and (1):CHCO(2)Et with 2,3-dimethylbutane in alkane vs 1:1 pentane-perfluorohexane solution. A solvent effect was observed in the reaction of (1):CHCO(2)Et, but not (1):CH2. The preference for tertiary/primary C-H insertion by (1):CHCO(2)Et is 3.97 +/- 0.04 in 2,3-dimethylbutane solution and 4.48 +/- 0.09 in 1:1 pentane-perfluorohexane solution. There is no change in the stereospecificity of(1):CHCO(2)Et addition to cis-2-pentene in pentane vs 1:1 pentane-perfluorohexane solution, indicating that the observed change in selectivity is probably not due to intersystem crossing to (3):CHCO(2)Et. Ab initio calculations provide evidence for a possible origin of the solvent effect via formation of carbene-fluoroalkane complexes. At the RHF/3-21G level, (1):CHCO(2)Me forms bound complexes with CH3F and CF4 with binding energies ranging from 5.7-19.6 kcal/mol. These complexes are 1.3-1.7 times more strongly bound than complexes formed between (1):CH2 and the same fluoroalkanes.
• Transition-Metal-Catalyzed Carbenoid Reactions of Sulfonium Ylides
  作者：Paul Müller、Daniel Fernandez、Patrice Nury、Jean-Claude Rossier

  DOI：10.1002/(sici)1522-2675(19990609)82:6<935::aid-hlca935>3.0.co;2-x

  日期：1999.6.9

  Olefins undergo cyclopropanation with diphenylsulfonium (ethoxycarbonyl)methylide (= diphenylsulfonium 2-ethoxy-2-oxoethylide; 3a) in the presence of chiral Cu-I or Rh-II catalysts, trans/cis Ratios and ee's of the cyclopropanes 6 obtained with this ylide in the presence of a chiral Cu-I catalyst 7 are identical with those obtained with ethyl diazoacetate (4). In the case of catalysis with Rh-II, the trans/cis ratios of the cyclopropanes as well as the enantioselectivity change slightly upon going from the ylide 3a to diazoacetate 4.