methyl 4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxobutanoate | 264601-64-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxobutanoate
• 英文别名: Methyl 4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]octan-1-yl)-3-oxobutanoate
• CAS: 264601-64-1
• 化学式: C₁₁H₁₆O₆
• 分子量: 244.244
• InChiKey: YABNRHWDYKLXCO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 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 4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxobutanoate 在 对甲苯磺酰叠氮 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以93%的产率得到methyl 2-diazo-4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxobutanoate
  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：

  methyl 3-methyloxetan-3-ylcarbinyl 3-oxopentane-1,5-dioate 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以55%的产率得到methyl 4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)-3-oxobutanoate
  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

• Synthesis of 1<i>H</i>-2-Benzopyran-5,8-dione Skeleton through a Cascade Reaction between Benzoquinone and β-Ketoester
  作者：Masataka Nakahara、Hiroyoshi Ohtsu、Masaki Kawano、Kengo Hanaya、Takeshi Sugai、Shuhei Higashibayashi

  DOI：10.1246/cl.210817

  日期：2022.4.5

  derivative and β-ketoesters under basic conditions. The reaction using potassium carbonate and 18-crown-6 in THF was the best condition, giving 1H-2-benzopyran-5,8-dione derivatives in good yields. The UV-vis absorption spectrum and cyclic voltammogram of the synthesized 1H-2-benzopyran-5,8-dione derivative were measured, clarifying the photophysical and redox properties.

  1 H -2-benzopyran-5,8-dione 结构是在碱性条件下通过Michael 加成、HBr 消除和二溴苯醌衍生物与β-酮酯之间的O-烷基化反应合成的。使用碳酸钾和 18-crown-6 在 THF 中的反应是最佳条件，以良好的收率得到 1 H -2-benzopyran-5,8-dione 衍生物。测定了合成的1 H -2-苯并吡喃-5,8-二酮衍生物的紫外-可见吸收光谱和循环伏安图，阐明了光物理和氧化还原性质。
• 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.