methyl <5a'S,6'R,9'S>-2-(3'H-3',6'-dimethyl-9a'-formyl-3'-hydroxyperhydro-1',2'-benzodioxepin-9'-yl)propenoate | 129143-91-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl <5a'S,6'R,9'S>-2-(3'H-3',6'-dimethyl-9a'-formyl-3'-hydroxyperhydro-1',2'-benzodioxepin-9'-yl)propenoate
• 英文别名: methyl 2-[(3R,5aS,6R,9S,9aR)-9a-formyl-3-hydroxy-3,6-dimethyl-5,5a,6,7,8,9-hexahydro-4H-benzo[c]dioxepin-9-yl]prop-2-enoate
• CAS: 129143-91-5
• 化学式: C₁₆H₂₄O₆
• 分子量: 312.363
• InChiKey: LPQGQQHWSJMALE-ZPPJNMKPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  82.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl <1'R,2'S,5'R,6'S>-2-<1'-formyl-1'-hydroperoxy-5'-methyl-6'-(3''-oxobutyl)cyclohex-2'-yl>propenoate 、 methyl <5a'S,6'R,9'S>-2-(3'H-3',6'-dimethyl-9a'-formyl-3'-hydroxyperhydro-1',2'-benzodioxepin-9'-yl)propenoate 、 对甲苯磺酸 以43%的产率得到
  参考文献：
  名称：

  HAYNES, RICHARD K.;VONWILLER, SIMONE C., J. CHEM. SOC. CHEM. COMMUN.,(1990) N, C. 451-453

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl artemisinate 在 tris(1,10-phenanthroline)iron(III) tris(hexafluorophosphate) 、 氧气 、 copper(II) bis(trifluoromethanesulfonate) 、 rose bengal 作用下， 以 乙腈 为溶剂， 反应 6.5h， 生成 methyl <5a'S,6'R,9'S>-2-(3'H-3',6'-dimethyl-9a'-formyl-3'-hydroxyperhydro-1',2'-benzodioxepin-9'-yl)propenoate
  参考文献：
  名称：

  Copper(II) Trifluoromethanesulfonate-Induced Cleavage Oxygenation of Allylic Hydroperoxides Derived from Qinghao Acid in the Synthesis of Qinghaosu Derivatives: Evidence for the Intermediacy of Enols

  摘要：

  The semisynthesis of qinghaosu (artemisinin) derivatives from qinghao (artemisinic) acid and related compounds is gaining increasing importance despite the fact that the key step in the transformation, the cleavage oxygenation of the intermediate allylic hydroperoxides to form peroxy hemiacetals, is not well understood. It has been found that the allylic hydroperoxide 10 derived from the methyl ester of qinghao acid under catalysis by trifluoromethanesulfonic acid (TfOH) in CH2Cl2 or copper(II) trifluoromethanesulfonate [Cu(OTf)(2)] in MeCN farms a thermally labile intermediate. Chromatographic isolation of the intermediate at low temperature and analysis by low-temperature H-1 and C-13 NMR spectroscopies showed it to be the simple enol 16a, a compound possessing unexpected stability. The enol 16a undergoes autoxidation at room temperature or facile oxygenation at -20 degrees C in the presence of Cu(II) and oxygen to give the peroxy hemiacetal 12. Thus, the catalyzed cleavage of cyclic allylic hydroperoxides proceeds via enol intermediates and it would seem that the propensity for subsequent oxygenation is related to the stability of the enol.

  DOI：

  10.1021/ja00150a009

文献信息

• HAYNES, RICHARD K.;VONWILLER, SIMONE C., J. CHEM. SOC. CHEM. COMMUN.,(1990) N, C. 451-453
  作者：HAYNES, RICHARD K.、VONWILLER, SIMONE C.

  DOI：——

  日期：——
• Copper(II) Trifluoromethanesulfonate-Induced Cleavage Oxygenation of Allylic Hydroperoxides Derived from Qinghao Acid in the Synthesis of Qinghaosu Derivatives: Evidence for the Intermediacy of Enols
  作者：Simone C. Vonwiller、Jacqueline A. Warner、Simon T. Mann、Richard K. Haynes

  DOI：10.1021/ja00150a009

  日期：1995.11

  The semisynthesis of qinghaosu (artemisinin) derivatives from qinghao (artemisinic) acid and related compounds is gaining increasing importance despite the fact that the key step in the transformation, the cleavage oxygenation of the intermediate allylic hydroperoxides to form peroxy hemiacetals, is not well understood. It has been found that the allylic hydroperoxide 10 derived from the methyl ester of qinghao acid under catalysis by trifluoromethanesulfonic acid (TfOH) in CH2Cl2 or copper(II) trifluoromethanesulfonate [Cu(OTf)(2)] in MeCN farms a thermally labile intermediate. Chromatographic isolation of the intermediate at low temperature and analysis by low-temperature H-1 and C-13 NMR spectroscopies showed it to be the simple enol 16a, a compound possessing unexpected stability. The enol 16a undergoes autoxidation at room temperature or facile oxygenation at -20 degrees C in the presence of Cu(II) and oxygen to give the peroxy hemiacetal 12. Thus, the catalyzed cleavage of cyclic allylic hydroperoxides proceeds via enol intermediates and it would seem that the propensity for subsequent oxygenation is related to the stability of the enol.