methyl 5-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxopentanoate | 264601-70-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 5-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxopentanoate
• 英文别名: Methyl 5-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)-3-oxopentanoate
• CAS: 264601-70-9
• 化学式: C₁₂H₁₈O₆
• 分子量: 258.271
• InChiKey: QNKSMZQTWZIVCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 5-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxopentanoate 在 dirhodium tetraacetate 、 对甲苯磺酰叠氮 、 potassium carbonate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.5h， 生成 1-methoxy-5-methoxycarbonyl-8-methyl-6,10,11-trioxabicyclo[6.2.2]dodecan-4-one
  参考文献：
  名称：

  Three- to Six-Carbon Ring-Enlargement Reaction of Cyclic Ortho Esters Bearing a Diazocarbonyl Side Chain. Use of the Intramolecular Formation of Tricyclooxonium Ylides

  摘要：

  Two types of bicyclic ortho esters 14 and 18, which are tethered to a diazocarbonyl group by polymethylene linkages -(CH2)(n)- of different lengths (n = 1-3 for 14 and 1-4 for 18), were prepared and catalytically decomposed by treatment with Rh-2(OAc)(4) either in the presence or absence of a protic nucleophile (MeOH, PhOH, AcOH) to give ring-enlargement product lactones 25 and 30 of different sizes. With 14, the enlargement took place when n = 1 or 2, but not when n = 3. With 18, in which the diazo carbon is substituted with a methoxycarbonyl group, the length of the chain can be extended further to n. = 4 to obtain ring-enlargement products or their derivatives. All of these reactions could be explained in terms of the intermediacy of tricyclooxonium ylides 22 and 28. The ylides form an equilibrium with the corresponding ring-opened zwitterions 22' and 28', respectively, which, after protonation by a protic nucleophile, undergo mainly ring-enlargement to form medium-sized or large oxalactones rather than 1,2-rearrangement.

  DOI：

  10.1021/jo991332t
• 作为产物：
  描述：

  5-methoxycarbonyl-4-oxopentanoic acid 在 4-二甲氨基吡啶 、 三氟化硼乙醚 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 生成 methyl 5-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxopentanoate
  参考文献：
  名称：

  Three- to Six-Carbon Ring-Enlargement Reaction of Cyclic Ortho Esters Bearing a Diazocarbonyl Side Chain. Use of the Intramolecular Formation of Tricyclooxonium Ylides

  摘要：

  Two types of bicyclic ortho esters 14 and 18, which are tethered to a diazocarbonyl group by polymethylene linkages -(CH2)(n)- of different lengths (n = 1-3 for 14 and 1-4 for 18), were prepared and catalytically decomposed by treatment with Rh-2(OAc)(4) either in the presence or absence of a protic nucleophile (MeOH, PhOH, AcOH) to give ring-enlargement product lactones 25 and 30 of different sizes. With 14, the enlargement took place when n = 1 or 2, but not when n = 3. With 18, in which the diazo carbon is substituted with a methoxycarbonyl group, the length of the chain can be extended further to n. = 4 to obtain ring-enlargement products or their derivatives. All of these reactions could be explained in terms of the intermediacy of tricyclooxonium ylides 22 and 28. The ylides form an equilibrium with the corresponding ring-opened zwitterions 22' and 28', respectively, which, after protonation by a protic nucleophile, undergo mainly ring-enlargement to form medium-sized or large oxalactones rather than 1,2-rearrangement.

  DOI：

  10.1021/jo991332t

文献信息

• Three- to Six-Carbon Ring-Enlargement Reaction of Cyclic Ortho Esters Bearing a Diazocarbonyl Side Chain. Use of the Intramolecular Formation of Tricyclooxonium Ylides
  作者：Akira Oku、Munenori Numata

  DOI：10.1021/jo991332t

  日期：2000.4.1

  Two types of bicyclic ortho esters 14 and 18, which are tethered to a diazocarbonyl group by polymethylene linkages -(CH2)(n)- of different lengths (n = 1-3 for 14 and 1-4 for 18), were prepared and catalytically decomposed by treatment with Rh-2(OAc)(4) either in the presence or absence of a protic nucleophile (MeOH, PhOH, AcOH) to give ring-enlargement product lactones 25 and 30 of different sizes. With 14, the enlargement took place when n = 1 or 2, but not when n = 3. With 18, in which the diazo carbon is substituted with a methoxycarbonyl group, the length of the chain can be extended further to n. = 4 to obtain ring-enlargement products or their derivatives. All of these reactions could be explained in terms of the intermediacy of tricyclooxonium ylides 22 and 28. The ylides form an equilibrium with the corresponding ring-opened zwitterions 22' and 28', respectively, which, after protonation by a protic nucleophile, undergo mainly ring-enlargement to form medium-sized or large oxalactones rather than 1,2-rearrangement.