Ethyl 2-oxo-2-phenylethyl diazomalonate | 125416-41-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Ethyl 2-oxo-2-phenylethyl diazomalonate
• 英文别名: 1-O-ethyl 3-O-phenacyl 2-diazopropanedioate
• CAS: 125416-41-3
• 化学式: C₁₃H₁₂N₂O₅
• 分子量: 276.249
• InChiKey: HCADGBZSTVLGCI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  71.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-Oxopropyl 2-diazo-3-oxobutanoate 、 Ethyl 2-oxo-2-phenylethyl diazomalonate 在 rhodium(II) acetate dimer 作用下， 以 苯 为溶剂， 反应 0.33h， 以94%的产率得到8-Acetyl-4,6-epoxy-4-methyl-2,3,3a,4,5,7,8,8a-octahydro-1,3,7-trioxo-N-phenyl-1H-oxepino<4,5-c>pyrrole
  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：

  Ethyl 2-oxo-2-phenylethyl malonate 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 乙腈 为溶剂， 以46%的产率得到Ethyl 2-oxo-2-phenylethyl diazomalonate
  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

• Carbonyl ylide formation from the rhodium (<scp>II</scp>) acetate catalysed reaction of keto α-diazoacetate derivatives
  作者：Dennis C. Dean、Keith E. Krumpe、Albert Padwa

  DOI：10.1039/c39890000921

  日期：——

  Formation of carbonyl ylides from the reaction of keto α-diazoacetates with rhodium (II) acetate has been found to be dependent on the electrophilicity of the intermediate rhodium carbenoid.

  已经发现由酮基α-重氮乙酸酯与乙酸铑（II）的反应形成羰基化物取决于中间铑类胡萝卜素的亲电性。
• DEAN, DENNIS C.;KRUMPA, KEITH E.;PADWA, ALBERT, J. CHEM. SOC. CHEM. COMMUN.,(1989) N4, C. 921-922
  作者：DEAN, DENNIS C.、KRUMPA, KEITH E.、PADWA, ALBERT

  DOI：——

  日期：——