(8S-cis)-8-acetyl-10-((3-amino-2,3,6-trideoxy-α-L-lyxohexopyranosyl)oxy)-6a,7,8,9,10,10a-hexahydro-5,8,12-trihydroxy-1-methoxy-6,11-naphthacenedione | 118868-84-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 蒽环类药物
• 英文名称: (8S-cis)-8-acetyl-10-((3-amino-2,3,6-trideoxy-α-L-lyxohexopyranosyl)oxy)-6a,7,8,9,10,10a-hexahydro-5,8,12-trihydroxy-1-methoxy-6,11-naphthacenedione
• 英文别名: (8S-cis)-8-acetyl-10-<(3-amino-2,3,6-trideoxy-α-L-lyxohexopyranosyl)oxy>-6a,7,8,9,10,10a-hexahydro-5,8,12-trihydroxy-1-methoxy-6,11-naphthacenedione；leucodaunomycin
• CAS: 118868-84-1；118918-82-4；118918-83-5；118918-84-6；125827-05-6
• 化学式: C₂₇H₃₁NO₁₀
• 分子量: 529.544
• InChiKey: QLWKYNBAIBSTSN-FBSVRPAXSA-N

物化性质

• 沸点：
  835.1±65.0 °C(Predicted)
• 密度：
  1.51±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.19
• 重原子数：
  38.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  185.84
• 氢给体数：
  5.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  (8S-cis)-8-acetyl-10-((3-amino-2,3,6-trideoxy-α-L-lyxohexopyranosyl)oxy)-6a,7,8,9,10,10a-hexahydro-5,8,12-trihydroxy-1-methoxy-6,11-naphthacenedione 生成 道诺霉素氢醌
  参考文献：
  名称：

  Leuco daunomycin, a tautomer of daunomycin hydroquinone

  摘要：

  DOI：

  10.1021/ja00185a066
• 作为产物：
  描述：

  柔红霉素 盐酸盐 在 盐酸 、 sodium dithionite 作用下， 以 水 为溶剂， 生成 (8S-cis)-8-acetyl-10-((3-amino-2,3,6-trideoxy-α-L-lyxohexopyranosyl)oxy)-6a,7,8,9,10,10a-hexahydro-5,8,12-trihydroxy-1-methoxy-6,11-naphthacenedione 、 2-acetyl-1,2,3,4,4a,12a-hexahydro-7-methoxy-2,6,11-trihydroxy-5,12-naphthacenedione
  参考文献：
  名称：

  Leuco daunomycin, a tautomer of daunomycin hydroquinone

  摘要：

  DOI：

  10.1021/ja00185a066

文献信息

• Leucodaunomycins, new intermediates in the redox chemistry of daunomycin
  作者：Donald M. Bird、Giorgio Gaudiano、Tad H. Koch

  DOI：10.1021/ja00001a044

  日期：1991.1

  The reduction of daunomycin (1a) to the hydroquinone state has been described in the literature as leading either to elimination of the sugar daunosamine with formation of of 7-deoxydaunomycinone (5) under anaerobic conditions or to subsequent oxidation by molecular oxygen, yielding reactive oxygen species under aerobic conditions. The conditions under which the hydroquinone of 1a (7) tautomerizes, producing an isolable reduced form of 1a, referred to as leucodaunomycin, (8S)-cis-8-acetyl-10-[(3-amino-2,3,6-trideoxy-alpha-L-lyxo-hexopyranosy)oxy]-6a,7,8,9,10,10a-hexahydro-5,8,12-trihydroxy-1-methoxy-6,11-naphthacenedione (3), are described here. The synthesis and characterization of the the four disastereomers, A-D, of 3, along with studies of aerobic and anaerobic chemistry of two isomers, A and C, are reported. Under aerobic conditions, the isomers of 3 react with oxygen to form 1a, 5, 7-epidaunomycinone (8), 7-deoxy-7-ketodaunomycinone (9), 7-deoxy-7,13-epidioxy-daunomycinol (10) and daunomycinone (6), and the rate constant is a function of ph and stereochemistry and varies from 3.0 x 10(-4) to 2.6 x 10(-2) s-1 at pH 7.4. Under anaerobic conditions at pH 7.4 and 25-degrees-C, an aqueous solution of isomer A of 3 forms at 97:3 ratio of 5 to 6, and the reaction follows consecutive first-order kinetics with a k1 of 1.0 x 10-(-2) S-1 for the tautomerization of 3 to hydroquinone 7 and a k2 of 3.3 x 10(-2) S-1 for the tauntomerization of quinone methide 2 to 5. Under identical conditions, isomer C of 3 forms a 96.4 ratio of 5 to 6, and the reaction follows first-order kinetics with a k of 1.2 x 10(-3) S-1 for tautomerization of 3 to 7. Finally, the ability of 3 to react with N-acetyl-L-cysteine and participate in an autocatalytic cycle in the presence of 1a to form 7-[(N-acetyl-L-cysteinyl)thio]-7-deoxydaunomycinone (11) is described.