1,1-Dimethyl-2-oxopropyl diazoacetate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1-Dimethyl-2-oxopropyl diazoacetate
• 英文别名: (2-Methyl-3-oxobutan-2-yl) 2-diazoacetate；(2-methyl-3-oxobutan-2-yl) 2-diazoacetate
• 化学式: C₇H₁₀N₂O₃
• 分子量: 170.168
• InChiKey: UQSVCFGKKGGPLV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  丁炔二酸二甲酯 、 1,1-Dimethyl-2-oxopropyl diazoacetate 在 rhodium(II) acetate dimer 作用下， 以 苯 为溶剂， 反应 1.0h， 以45%的产率得到Cyclohepta-2,4,6-trienecarboxylic acid 1,1-dimethyl-2-oxo-propyl ester
  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：

  3-羟基-3-甲基-2-丁酮 、 4-甲基-2-(2-氯代-2-氧代乙亚甲基)苯磺酰肼 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以21%的产率得到1,1-Dimethyl-2-oxopropyl diazoacetate
  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