Methyl (8aS)-3-acetyl-4,7,7-trioxo-1,4,6,7,8,8a-hexahydro-7λ⁶-<1,3>thiazolo<4,3-c><1,2,4>triazine-8a-carboxylate | 229306-83-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Methyl (8aS)-3-acetyl-4,7,7-trioxo-1,4,6,7,8,8a-hexahydro-7λ⁶-<1,3>thiazolo<4,3-c><1,2,4>triazine-8a-carboxylate
• 英文别名: methyl (8aS)-3-acetyl-4,7,7-trioxo-6,8-dihydro-1H-[1,3]thiazolo[4,3-c][1,2,4]triazine-8a-carboxylate
• CAS: 229306-83-6
• 化学式: C₉H₁₁N₃O₆S
• 分子量: 289.269
• InChiKey: SCUWAVOOTIKQHE-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  131
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Methyl (8aS)-3-acetyl-4,7,7-trioxo-1,4,6,7,8,8a-hexahydro-7λ⁶-<1,3>thiazolo<4,3-c><1,2,4>triazine-8a-carboxylate 在 甲酸 、 水 、 双氧水 作用下， 反应 15.0h， 以62%的产率得到Methyl (8aS)-3,4,7,7-tetraoxoperhydro-7λ⁶-<1,3>thiazolo<4,3-c><1,2,4>triazine-8a-carboxylate
  参考文献：
  名称：

  ‘Hidden’ axial chirality as a stereodirecting element in reactions involving enol(ate) intermediates. Part 2.† Cyclisation reactions of methyl (4R)-3-(2-diazo-3-oxobutanoyl)-1,1-dioxo-1λ6,3- (and 1-oxo-1λ4,3-) thiazolidine-4-carboxylates

  摘要：

  -[1,3]thiazolo[4,3-c][1(2,4)]triazine-8a-carboxylate 16。

  DOI：

  10.1039/a900280d
• 作为产物：
  描述：

  methyl (4R)-3-(2-diazo-3-oxobutanoyl)thiazolidine-4-carboxylate 在 三乙胺 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 反应 16.0h， 生成 Methyl (8aS)-3-acetyl-4,7,7-trioxo-1,4,6,7,8,8a-hexahydro-7λ⁶-<1,3>thiazolo<4,3-c><1,2,4>triazine-8a-carboxylate
  参考文献：
  名称：

  ‘Hidden’ axial chirality as a stereodirecting element in reactions involving enol(ate) intermediates. Part 2.† Cyclisation reactions of methyl (4R)-3-(2-diazo-3-oxobutanoyl)-1,1-dioxo-1λ6,3- (and 1-oxo-1λ4,3-) thiazolidine-4-carboxylates

  摘要：

  -[1,3]thiazolo[4,3-c][1(2,4)]triazine-8a-carboxylate 16。

  DOI：

  10.1039/a900280d

文献信息

• ‘Hidden’ axial chirality as a stereodirecting element in reactions involving enol(ate) intermediates. Part 2.† Cyclisation reactions of methyl (4R)-3-(2-diazo-3-oxobutanoyl)-1,1-dioxo-1λ6,3- (and 1-oxo-1λ4,3-) thiazolidine-4-carboxylates
  作者：Michael J. Betts、Robin G. Pritchard、Anthony Schofield、Richard J. Stoodley、Shaheen Vohra

  DOI：10.1039/a900280d

  日期：——

  Methyl (4R)-3-(2-diazo-3-oxobutanoyl)-1,1-dioxo-1λ6,3-thiazolidine-4-carboxylate 14 undergoes a base-induced cyclisation to give methyl (8aS)-3-acetyl-4,7,7-trioxo-1,4,6,7,8,8a-hexahydro-7λ6-[1,3]thiazolo[4,3-c][1,2,4]triazine-8a-carboxylate 15 in a state of high enantiomeric purity. Similar stereoselective cyclisations, proceeding with retention of configuration, are observed with methyl (1R,4R)- and (1S,4R)-3-(2-diazo-3-oxobutanoyl)-1-oxo-1λ4,3-thiazolidine-4-carboxylates 25 and 27 to give compounds 33 and 34. It is suggested that the cyclisation reactions proceed by way of planar ester enol(ate) intermediates which possess axial chirality, e.g. 35.The bicyclic sulfone 15 and the bicyclic sulfoxides 33 and 34 are also produced by oxidation of methyl (8aS)-3-acetyl-4-oxo-1,4,8,8a-tetrahydro[1,3]thiazolo[4,3-c][1,2,4]triazine-8a-carboxylate 5 with m-chloroperoxybenzoic acid (in DMF in the case of the sulfone 15 and in CHCl3 in the case of the sulfoxides 33 and 34). The use of the oxidant in methanol or of hydrogen peroxide in formic acid leads to an oxidative deacetylation to give methyl (8aS)-3,4,7,7-tetraoxoperhydro-7λ6-[1,3]thiazolo[4,3-c][1,2,4]triazine-8a-carboxylate 17, the structure of which is established by an X-ray crystallographic analysis. The analysis reveals an interesting packing arrangement of the molecules in the crystal, attributable to an intermolecular H-bonding network. In particular, intermolecular H-bonding between the ester carbonyl oxygen atom and the amino hydrogen atom at position 1 provides a possible explanation for the shift of the ester carbonyl absorption to 1680 cm–1 in the solid-state IR spectrum of compound 17.

  -[1,3]thiazolo[4,3-c][1(2,4)]triazine-8a-carboxylate 16。