[2-[(1R,2S,5S,6S,9S,10S,12R,13R,15S)-15-acetyloxy-13-bromo-5-methyl-19-oxapentacyclo[10.5.2.01,13.02,10.05,9]nonadecan-6-yl]-2-oxoethyl] acetate | 162828-33-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: [2-[(1R,2S,5S,6S,9S,10S,12R,13R,15S)-15-acetyloxy-13-bromo-5-methyl-19-oxapentacyclo[10.5.2.01,13.02,10.05,9]nonadecan-6-yl]-2-oxoethyl] acetate
• CAS: 162828-33-3
• 化学式: C₂₅H₃₅BrO₆
• 分子量: 511.453
• InChiKey: NLQDDECCCXUFGA-YUCDHIDUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  [2-[(1R,2S,5S,6S,9S,10S,12R,13R,15S)-15-acetyloxy-13-bromo-5-methyl-19-oxapentacyclo[10.5.2.01,13.02,10.05,9]nonadecan-6-yl]-2-oxoethyl] acetate 在 吡啶 、 氢氧化钾 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.25h， 生成 21-acetoxy-5-bromo-6β,19-epoxy-3β-hydroxy-5α-pregnan-20-one
  参考文献：
  名称：

  Syntheses of 21-hydroxy-11,19-oxidopregn-4-ene-3,20-dione and 21-hydroxy-6,19-oxidopregn-4-ene-3,20-dione

  摘要：

  The 21-hydroxy analogues of 11,19-oxidoprogesterone and 6,19-oxidoprogesterone have been synthesized from readily available materials. Hydroxylation at C-21 was effected with iodosobenzene (from phenyliodosodiacetate and methanolic potassium hydroxide) on a 20-ketopregnane. For the 11,19-oxido derivative, the hydroxylation was carried our on a precursor containing the oxide-bridge. This approach was not adequate for the 6,19-oxido steroid due to the very low yields encountered; hence in the latter case the order of introduction of the C-21 functionality and the oxide-bridge was reversed.

  DOI：

  10.1016/0039-128x(94)00052-e
• 作为产物：
  描述：

  21-羟基孕烯醇酮 在 吡啶 、 高氯酸 、 碘 、 mercury(II) oxide 、 N-溴代乙酰胺 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醚 为溶剂， 反应 0.5h， 生成 [2-[(1R,2S,5S,6S,9S,10S,12R,13R,15S)-15-acetyloxy-13-bromo-5-methyl-19-oxapentacyclo[10.5.2.01,13.02,10.05,9]nonadecan-6-yl]-2-oxoethyl] acetate
  参考文献：
  名称：

  Syntheses of 21-hydroxy-11,19-oxidopregn-4-ene-3,20-dione and 21-hydroxy-6,19-oxidopregn-4-ene-3,20-dione

  摘要：

  The 21-hydroxy analogues of 11,19-oxidoprogesterone and 6,19-oxidoprogesterone have been synthesized from readily available materials. Hydroxylation at C-21 was effected with iodosobenzene (from phenyliodosodiacetate and methanolic potassium hydroxide) on a 20-ketopregnane. For the 11,19-oxido derivative, the hydroxylation was carried our on a precursor containing the oxide-bridge. This approach was not adequate for the 6,19-oxido steroid due to the very low yields encountered; hence in the latter case the order of introduction of the C-21 functionality and the oxide-bridge was reversed.

  DOI：

  10.1016/0039-128x(94)00052-e

文献信息

• Ultrasound assisted remote functionalization of non-activated carbon atoms: efficient in situ formation of tetrahydrofurans by sonolysis of bromohydrins with
  作者：Saul C.P. Costa、M.J.S.Miranda Moreno、M.Luisa Sáe Melo、AndréS. Campos Neves

  DOI：10.1016/s0040-4039(99)01849-3

  日期：1999.12

  Ultrasonic irradiation of bromohydrins in the presence of (diacetoxyiodo)benzene and I2 generates alkoxyl radicals which lead in situ to intramolecular hydrogen abstraction on the C-19 non-activated carbon atoms in steroids producing tetrahydrofurans selectively in very good yields. Photolysis was less effective in promoting such conversions.

  在（二乙酰氧基碘）苯和I 2的存在下对溴代醇进行超声波照射会生成烷氧基，这些自由基会原位导致类固醇中C-19非活化碳原子上的分子内氢抽象，并以非常高的收率选择性地产生四氢呋喃。光解作用在促进这种转化方面不太有效。