2-Propenyl <2-(1-oxo-1-phenylethyl)> propanedioate | 143888-55-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Propenyl <2-(1-oxo-1-phenylethyl)> propanedioate
• 英文别名: 2-Propenyl 2-oxo-2-phenylethyl malonate；3-O-phenacyl 1-O-prop-2-enyl propanedioate
• CAS: 143888-55-5
• 化学式: C₁₄H₁₄O₅
• 分子量: 262.262
• InChiKey: YMJUVTANXTZIBN-UHFFFAOYSA-N

物化性质

• 沸点：
  373.1±22.0 °C(Predicted)
• 密度：
  1.181±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Propenyl <2-(1-oxo-1-phenylethyl)> propanedioate 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以67%的产率得到2-Propenyl <2-(1-oxo-1-phenylethyl)> diazopropanedioate
  参考文献：
  名称：

  Stereo and electronic effects in the rhodium(II)-mediated synthesis of polycyclic lactones and lactams from .alpha.-diazo ester and amide precursors

  摘要：

  The rhodium(II) carboxylate catalyzed decomposition of several alpha-diazo esters and amides has been studied. A series of 5-keto-1-diazo acetates were prepared by acylation of alpha-hydroxy ketones using the (p-toluenesulfonyl)hydrazone of glyoxylic acid chloride. Treatment of these compounds with Rh(II) acetate afforded products derived from carbenoid insertion into solvent. When the hydrogen atom of the diazo carbon was replaced with an electron-withdrawing substituent, smooth cyclization occurred to produce a carbonyl ylide dipole which was subsequently trapped with different dipolarophiles. A series of N-alkyl-2-diazo-3-oxobutylamides, when treated with a catalytic quantity of rhodium(II) acetate, gave furo[3,4-c]furans in good yield. The reaction proceeds via addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. N-Alkynyl-substituted 2-diazoacetamides were also found to cyclize onto the tethered alkyne unit. The resulting rhodium carbenoid can undergo intramolecular and bimolecular cyclopropanation depending on both electronic and conformational factors. Rotamer population of the starting diazoamide was also found to influence product distribution.

  DOI：

  10.1021/jo00069a030
• 作为产物：
  描述：

  monoallyl malonate 、 2-羟基苯乙酮 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 以23%的产率得到2-Propenyl <2-(1-oxo-1-phenylethyl)> propanedioate
  参考文献：
  名称：

  Stereo and electronic effects in the rhodium(II)-mediated synthesis of polycyclic lactones and lactams from .alpha.-diazo ester and amide precursors

  摘要：

  The rhodium(II) carboxylate catalyzed decomposition of several alpha-diazo esters and amides has been studied. A series of 5-keto-1-diazo acetates were prepared by acylation of alpha-hydroxy ketones using the (p-toluenesulfonyl)hydrazone of glyoxylic acid chloride. Treatment of these compounds with Rh(II) acetate afforded products derived from carbenoid insertion into solvent. When the hydrogen atom of the diazo carbon was replaced with an electron-withdrawing substituent, smooth cyclization occurred to produce a carbonyl ylide dipole which was subsequently trapped with different dipolarophiles. A series of N-alkyl-2-diazo-3-oxobutylamides, when treated with a catalytic quantity of rhodium(II) acetate, gave furo[3,4-c]furans in good yield. The reaction proceeds via addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. N-Alkynyl-substituted 2-diazoacetamides were also found to cyclize onto the tethered alkyne unit. The resulting rhodium carbenoid can undergo intramolecular and bimolecular cyclopropanation depending on both electronic and conformational factors. Rotamer population of the starting diazoamide was also found to influence product distribution.

  DOI：

  10.1021/jo00069a030

文献信息

• Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with intramolecular cycloadditions
  作者：Albert Padwa、Susan F. Hornbuckle、Glen E. Fryxell、Zhijia J. Zhang

  DOI：10.1021/jo00047a032

  日期：1992.10

  A series of 5-alkenyl-1-diazo-2,5-pentanediones, when treated with a catalytic quantity of rhodium(II) acetate, were found to give cycloadducts derived from the intramolecular trapping of a carbonyl ylide intermediate. Tethers of three or four methylenes readily enter into intramolecular cycloaddition, while longer and shorter tethers were reluctant to do so. Alkenes attached to the formally cationic terminus of the carbonyl ylide readily undergo internal cycloaddition if the tether allows for a relatively strain-free transition state. The internal cycloaddition reaction does not occur when the olefinic side chain is attached by means of an ester functionality. Bimolecular trapping experiments established that carbonyl ylide formation occurred, but the dipole does not undergo intramolecular cycloaddition. The inability of these alpha-diazo keto esters to undergo internal cycloaddition is related to conformational factors. The equilibrium between the two possible conformations of the dipole lies predominantly on the side of the Z-isomer. In this orientation, intramolecular dipolar cycloaddition cannot occur, and instead the dipole collapses by means of a proton transfer to give an enol ether.
• Stereo and electronic effects in the rhodium(II)-mediated synthesis of polycyclic lactones and lactams from .alpha.-diazo ester and amide precursors
  作者：Albert Padwa、Dennis C. Dean、David J. Fairfax、Simon L. Xu

  DOI：10.1021/jo00069a030

  日期：1993.8

  The rhodium(II) carboxylate catalyzed decomposition of several alpha-diazo esters and amides has been studied. A series of 5-keto-1-diazo acetates were prepared by acylation of alpha-hydroxy ketones using the (p-toluenesulfonyl)hydrazone of glyoxylic acid chloride. Treatment of these compounds with Rh(II) acetate afforded products derived from carbenoid insertion into solvent. When the hydrogen atom of the diazo carbon was replaced with an electron-withdrawing substituent, smooth cyclization occurred to produce a carbonyl ylide dipole which was subsequently trapped with different dipolarophiles. A series of N-alkyl-2-diazo-3-oxobutylamides, when treated with a catalytic quantity of rhodium(II) acetate, gave furo[3,4-c]furans in good yield. The reaction proceeds via addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. N-Alkynyl-substituted 2-diazoacetamides were also found to cyclize onto the tethered alkyne unit. The resulting rhodium carbenoid can undergo intramolecular and bimolecular cyclopropanation depending on both electronic and conformational factors. Rotamer population of the starting diazoamide was also found to influence product distribution.