(2R,3S,5α,22R,23R,24R)-25-aza-6,6-(ethylenedioxy)-2,3-(isopropylidenedioxy)ergostane-22,23-diol | 244076-59-3

• 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: (2R,3S,5α,22R,23R,24R)-25-aza-6,6-(ethylenedioxy)-2,3-(isopropylidenedioxy)ergostane-22,23-diol
• 英文别名: (2R,3R,4R,5S)-2-(dimethylamino)-5-[(1'S,2'R,4'R,8'S,10'S,13'S,14'S,17'R,18'S)-2',6',6',18'-tetramethylspiro[1,3-dioxolane-2,11'-5,7-dioxapentacyclo[11.7.0.02,10.04,8.014,18]icosane]-17'-yl]hexane-3,4-diol
• CAS: 244076-59-3
• 化学式: C₃₂H₅₅NO₆
• 分子量: 549.792
• InChiKey: MYYFVJZBGJKDFV-FVGOIMLASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  39
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  80.6
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2R,3S,5α,22R,23R,24R)-25-aza-6,6-(ethylenedioxy)-2,3-(isopropylidenedioxy)ergostane-22,23-diol 在 吡啶 、 4-二甲氨基吡啶 、 三氟过氧乙酸 、 溶剂黄146 、 三氟乙酸 作用下， 以 氯仿 为溶剂， 反应 10.0h， 生成 (1R,3aS,3bS,6aS,8S,9R,10aR,10bS,12aS)-1-((1S,2R,3R,4R)-4-Dimethylamino-2,3-dihydroxy-1-methyl-pentyl)-8,9-dihydroxy-10a,12a-dimethyl-hexadecahydro-6-oxa-benzo[3,4]cyclohepta[1,2-e]inden-5-one
  参考文献：
  名称：

  Synthesis and Biological Activity of 25-Methoxy-, 25-Fluoro-, and 25-Azabrassinolide and 25-Fluorocastasterone:  Surprising Effects of Heteroatom Substituents at C-25

  摘要：

  The CuCN-catalyzed addition of 2-propenylmagnesium bromide to (threo-2R,3S,5 alpha,22R,23R,24S)-23,24-epoxy-6,6-(ethylenedioxy)-2,3-(isopropylidenedioxy)-26,27-dinorcholestan-22-ol (11a) afforded the corresponding Delta(25)-22,23-diol 12. This was converted into 25-methoxybrassinolide (7) by protection as the 22,23-acetonide 13, oxymercuration in methanol, Baeyer-Villiger oxidation, and deprotection. Similarly, the addition of pyridinium poly(hydrogen fluoride) Do 13 and deprotection afforded 25-fluorocastasterone (8), which was converted into 25-fluorobrassinolide (9) by Baeyer-Villiger oxidation. Treatment of threo-epoxide 11a with Me2NMgBr, followed by Baeyer-Villiger oxidation of the corresponding tetraacetate and saponification, provided 25-azabrassinolide (10). Epoxide 11a is therefore a versatile intermediate for the synthesis of side-chain analogues of brassinolide (1). 25-Methoxybrassinolide (7) displayed strong activity in the rice leaf lamina inclination bioassay, which was significantly enhanced by the simultaneous application of an auxin, indole-3-acetic acid (IAA). Thus, the presence of a 25-methoxy substituent, like that of the previously reported 25-hydroxy group in the 24-epibrassinolide series, yields a molecule with potent biological activity. On the other hand, 8-10 showed no bioactivity with or without IAA. This suggests that either the 25-fluoro and 25-aza substituents interfere with binding to a putative brassinosteroid receptor or that they prevent the in vivo enzymatic oxidation at C-25 that is required for bioactivity.

  DOI：

  10.1021/jo990312o
• 作为产物：
  描述：

  二甲胺 、 (2R,3S,5α,22R,23RS,24SR)-23,24-epoxy-6,6-(ethylenedioxy)-2,3-(isopropylidenedioxy)-26,27-dinorcholestan-22-ol 在 己基溴化镁 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以375 mg的产率得到(2R,3S,5α,22R,23R,24R)-25-aza-6,6-(ethylenedioxy)-2,3-(isopropylidenedioxy)ergostane-22,23-diol
  参考文献：
  名称：

  Synthesis and Biological Activity of 25-Methoxy-, 25-Fluoro-, and 25-Azabrassinolide and 25-Fluorocastasterone:  Surprising Effects of Heteroatom Substituents at C-25

  摘要：

  The CuCN-catalyzed addition of 2-propenylmagnesium bromide to (threo-2R,3S,5 alpha,22R,23R,24S)-23,24-epoxy-6,6-(ethylenedioxy)-2,3-(isopropylidenedioxy)-26,27-dinorcholestan-22-ol (11a) afforded the corresponding Delta(25)-22,23-diol 12. This was converted into 25-methoxybrassinolide (7) by protection as the 22,23-acetonide 13, oxymercuration in methanol, Baeyer-Villiger oxidation, and deprotection. Similarly, the addition of pyridinium poly(hydrogen fluoride) Do 13 and deprotection afforded 25-fluorocastasterone (8), which was converted into 25-fluorobrassinolide (9) by Baeyer-Villiger oxidation. Treatment of threo-epoxide 11a with Me2NMgBr, followed by Baeyer-Villiger oxidation of the corresponding tetraacetate and saponification, provided 25-azabrassinolide (10). Epoxide 11a is therefore a versatile intermediate for the synthesis of side-chain analogues of brassinolide (1). 25-Methoxybrassinolide (7) displayed strong activity in the rice leaf lamina inclination bioassay, which was significantly enhanced by the simultaneous application of an auxin, indole-3-acetic acid (IAA). Thus, the presence of a 25-methoxy substituent, like that of the previously reported 25-hydroxy group in the 24-epibrassinolide series, yields a molecule with potent biological activity. On the other hand, 8-10 showed no bioactivity with or without IAA. This suggests that either the 25-fluoro and 25-aza substituents interfere with binding to a putative brassinosteroid receptor or that they prevent the in vivo enzymatic oxidation at C-25 that is required for bioactivity.

  DOI：

  10.1021/jo990312o