2-Diazo-5-(2-methyl-[1,3]dioxolan-2-yl)-3-oxo-pentanoic acid methyl ester | 181180-17-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 2-Diazo-5-(2-methyl-[1,3]dioxolan-2-yl)-3-oxo-pentanoic acid methyl ester
• 英文别名: Methyl 2-diazo-5-(2-methyl-1,3-dioxolan-2-yl)-3-oxopentanoate；methyl 2-diazo-5-(2-methyl-1,3-dioxolan-2-yl)-3-oxopentanoate
• CAS: 181180-17-6
• 化学式: C₁₀H₁₄N₂O₅
• 分子量: 242.232
• InChiKey: ZTSQLDGZXLYNCM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  63.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-Diazo-5-(2-methyl-[1,3]dioxolan-2-yl)-3-oxo-pentanoic acid methyl ester 在 六氟乙酰丙酮化铜的水合物 作用下， 以 苯 为溶剂， 反应 12.0h， 以50%的产率得到(+/-)-(1S,6S)-6-(carboxymethyl)-1-methyl-7-oxo-2,5-dioxabicyclo[4.3.0]nonane
  参考文献：
  名称：

  Study of the Rearrangements of Oxonium Ylides Generated from Ketals

  摘要：

  Intramolecular exposure of cyclic ketals to metal carbenoids generates a proposed oxonium ylide intermediate that subsequently rearranges to one of three general products. The product resulting from a 1,2-shift to the ketal carbon is favored by larger ketals that lack radical stabilizing groups. A bridged bicyclic structure is formed by competitive 1,2-shift to the exocyclic carbon of the ketal and is favored by smaller ketal ring sizes that possess radical-stabilizing groups. An alternative beta-elimination pathway can also operate when neither of the 1,2-shift pathways are favored. The enol ether that is formed in this latter pathway rearranges easily to an isomeric dioxene.

  DOI：

  10.1021/jo961896m
• 作为产物：
  描述：

  乙酰丙酸甲酯 在 氢氧化钾 、 4-羧基苯磺叠氮 、 对甲苯磺酸 、 三乙胺 、 N,N'-羰基二咪唑 、 原甲酸三甲酯 作用下， 以 乙腈 、 苯 为溶剂， 反应 36.5h， 生成 2-Diazo-5-(2-methyl-[1,3]dioxolan-2-yl)-3-oxo-pentanoic acid methyl ester
  参考文献：
  名称：

  Study of the Rearrangements of Oxonium Ylides Generated from Ketals

  摘要：

  Intramolecular exposure of cyclic ketals to metal carbenoids generates a proposed oxonium ylide intermediate that subsequently rearranges to one of three general products. The product resulting from a 1,2-shift to the ketal carbon is favored by larger ketals that lack radical stabilizing groups. A bridged bicyclic structure is formed by competitive 1,2-shift to the exocyclic carbon of the ketal and is favored by smaller ketal ring sizes that possess radical-stabilizing groups. An alternative beta-elimination pathway can also operate when neither of the 1,2-shift pathways are favored. The enol ether that is formed in this latter pathway rearranges easily to an isomeric dioxene.

  DOI：

  10.1021/jo961896m

文献信息

• Selectivity in the rearrangements of oxonium ylides
  作者：John B. Brogan、Cary B. Bauer、Robin D. Rogers、Charles K. Zercher

  DOI：10.1016/0040-4039(96)01015-5

  日期：1996.7

  Oxonium ylides were formed via an intramolecular reaction between a series of dioxalanes and metallocarbenes. The substitution patterns present in the ketals greatly affect the rearrangements of the oxonium ylides. It was also demonstrated that electron-deficient copper (II) species are superior catalysts for these systems.

  氧化盐是通过一系列二恶烷和茂金属之间的分子内反应形成的。存在于缩酮中的取代模式极大地影响了氧代鎓叶立德的重排。还证明了缺电子的铜（II）物种是这些系统的优良催化剂。
• Study of the Rearrangements of Oxonium Ylides Generated from Ketals
  作者：John B. Brogan、Charles K. Zercher、Cary B. Bauer、Robin D. Rogers

  DOI：10.1021/jo961896m

  日期：1997.6.13

  Intramolecular exposure of cyclic ketals to metal carbenoids generates a proposed oxonium ylide intermediate that subsequently rearranges to one of three general products. The product resulting from a 1,2-shift to the ketal carbon is favored by larger ketals that lack radical stabilizing groups. A bridged bicyclic structure is formed by competitive 1,2-shift to the exocyclic carbon of the ketal and is favored by smaller ketal ring sizes that possess radical-stabilizing groups. An alternative beta-elimination pathway can also operate when neither of the 1,2-shift pathways are favored. The enol ether that is formed in this latter pathway rearranges easily to an isomeric dioxene.