3-methyloxetan-3-yl-carbinyl 5-oxohexanoate | 264601-56-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 3-methyloxetan-3-yl-carbinyl 5-oxohexanoate
• 英文别名: (3-Methyloxetan-3-yl)methyl 5-oxohexanoate
• CAS: 264601-56-1
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: CHDPNPAQEGNJGQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-methyloxetan-3-yl-carbinyl 5-oxohexanoate 在 三氟乙酸2,2,2-三氟乙酯 、 三氟化硼乙醚 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 22.67h， 生成 1-diazo-5-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)pentan-2-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：

  3-甲基-3-羟甲基氧杂环丁烷 、 5-氧代己酸 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以96%的产率得到3-methyloxetan-3-yl-carbinyl 5-oxohexanoate
  参考文献：
  名称：

  Efficient total synthesis of 5-oxo-6(E),8(Z),11(Z),14(Z)-eicosatetraenoic acid (5-oxo-ETE), a potent proinflammatory autacoid

  摘要：

  The title eicosanoid was prepared in good overall yield via a convergent aldol strategy that obviates the need for HPLC separation of olefinic isomers. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00668-2

文献信息

• Efficient total synthesis of 5-oxo-6(E),8(Z),11(Z),14(Z)-eicosatetraenoic acid (5-oxo-ETE), a potent proinflammatory autacoid
  作者：Suchismita Mohapatra、Jorge H Capdevila、Robert C Murphy、John M Hevko、J.R Falck

  DOI：10.1016/s0040-4039(01)00668-2

  日期：2001.6

  The title eicosanoid was prepared in good overall yield via a convergent aldol strategy that obviates the need for HPLC separation of olefinic isomers. (C) 2001 Elsevier Science Ltd. All rights reserved.
• 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.