methyl 6-acetoxy-6-methoxy-1-oxo-2,4-cyclohexadiene-5-carboxylate | 132019-87-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-acetoxy-6-methoxy-1-oxo-2,4-cyclohexadiene-5-carboxylate
• 英文别名: Methyl 6-acetyloxy-6-methoxy-5-oxocyclohexa-1,3-diene-1-carboxylate
• CAS: 132019-87-5
• 化学式: C₁₁H₁₂O₆
• 分子量: 240.213
• InChiKey: MPIVGCHFPRRTDI-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：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 6-acetoxy-6-methoxy-1-oxo-2,4-cyclohexadiene-5-carboxylate 在 K₂HPO₃-deactivated silica gel 、 四丁基碘化铵 、 二异丁基氢化铝 、 potassium carbonate 作用下， 以 二甲基亚砜 、 甲苯 为溶剂， 反应 73.5h， 生成 1-benzoxy-2,6-dimethoxy-3-(hydroxymethyl)-8-(methoxymethoxy)naphthalene
  参考文献：
  名称：

  Synthesis of Helically Chiral Molecules: Stereoselective Total Synthesis of the Perylenequinones Phleichrome and Calphostin A

  摘要：

  The total syntheses of the perylenequinone natural products phleichrome and calphostin A are detailed. The syntheses were based on (1) the de novo construction of regiospecifically oxygenated and selectively protected naphthalene subunits, (2) the enantiospecific introduction of the stereogenic side chains using a chiral (alpha-alkoxyalkyl)-lithium reagent, and (3) a highly atropdiastereoselective Cu(I)-promoted biaryl synthesis for the stereoselective introduction of the helical axis of the calphostins. The total syntheses were achieved in 13 or 14 steps, respectively, with excellent control of absolute stereochemistry.

  DOI：

  10.1021/ja00149a012
• 作为产物：
  描述：

  苯甲酸,二羟基- 在 盐酸 、 palladium on activated charcoal 氢气 、 sodium hydride 作用下， 以 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 25.0~70.0 ℃ 、98.06 kPa 条件下， 生成 methyl 6-acetoxy-6-methoxy-1-oxo-2,4-cyclohexadiene-5-carboxylate
  参考文献：
  名称：

  An efficient synthesis of the naphthalene subunits of the protein kinase C inhibitor calphostin C

  摘要：

  An efficient synthesis of bromonaphthalenes 5b-c, which represent suitably functionalized precursors to the perylenequinone ring system characteristic of the protein kinase C inhibitor calphostin C (1), is described and was based on the Diels-Alder reaction of omicron-quinol acetate 7 with 1,1,3-trioxygenated butadienes 6a-c, followed by selective, acid-promoted elimination of R3SiOH and AcOH to directly afford naphthalenes 11a-c.

  DOI：

  10.1021/jo00004a006

文献信息

• Atropdiastereoselective Total Synthesis of Phleichrome and the Protein Kinase C Inhibitor Calphostin A
  作者：Robert S. Coleman、Eugene B. Grant

  DOI：10.1021/ja00098a043

  日期：1994.9
• COLEMAN, ROBERT S.;GRANT, EUGENE B., J. ORG. CHEM., 56,(1991) N, C. 1357-1359
  作者：COLEMAN, ROBERT S.、GRANT, EUGENE B.

  DOI：——

  日期：——
• An efficient synthesis of the naphthalene subunits of the protein kinase C inhibitor calphostin C
  作者：Robert S. Coleman、Eugene B. Grant

  DOI：10.1021/jo00004a006

  日期：1991.2

  An efficient synthesis of bromonaphthalenes 5b-c, which represent suitably functionalized precursors to the perylenequinone ring system characteristic of the protein kinase C inhibitor calphostin C (1), is described and was based on the Diels-Alder reaction of omicron-quinol acetate 7 with 1,1,3-trioxygenated butadienes 6a-c, followed by selective, acid-promoted elimination of R3SiOH and AcOH to directly afford naphthalenes 11a-c.
• Synthesis of Helically Chiral Molecules: Stereoselective Total Synthesis of the Perylenequinones Phleichrome and Calphostin A
  作者：Robert S. Coleman、Eugene B. Grant

  DOI：10.1021/ja00149a012

  日期：1995.11

  The total syntheses of the perylenequinone natural products phleichrome and calphostin A are detailed. The syntheses were based on (1) the de novo construction of regiospecifically oxygenated and selectively protected naphthalene subunits, (2) the enantiospecific introduction of the stereogenic side chains using a chiral (alpha-alkoxyalkyl)-lithium reagent, and (3) a highly atropdiastereoselective Cu(I)-promoted biaryl synthesis for the stereoselective introduction of the helical axis of the calphostins. The total syntheses were achieved in 13 or 14 steps, respectively, with excellent control of absolute stereochemistry.