4-O-[(2R,3S,4R,5S,6R)-5-[diethyl(propan-2-yl)silyl]oxy-6-methyl-4-[(2-phenylacetyl)amino]-2-[[(1R,3S,7R,8R,11R,15R,19S,20S,21R,22S,23E,25E,27E,29E,31E,33E,35E,37R,39S,40S,41S)-8,21,41-tris[[diethyl(propan-2-yl)silyl]oxy]-1-methoxy-40-methoxycarbonyl-5,13-bis(4-methoxyphenyl)-19,20,22-trimethyl-17-oxo-4,6,12,14,18,43-hexaoxatetracyclo[37.3.1.13,7.111,15]pentatetraconta-23,25,27,29,31,33,35-heptaen-37-yl]oxy]oxan-3-yl] 1-O-[(3S,9S,10R,13R,14R,17R)-17-[(E,2R,5R)-5,6-dimethylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,9,11,12,14,15,16,17-decahydro-1H-cyclopenta[a]phenanthren-3-yl] butanedioate | 1415683-21-4

• 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: 4-O-[(2R,3S,4R,5S,6R)-5-[diethyl(propan-2-yl)silyl]oxy-6-methyl-4-[(2-phenylacetyl)amino]-2-[[(1R,3S,7R,8R,11R,15R,19S,20S,21R,22S,23E,25E,27E,29E,31E,33E,35E,37R,39S,40S,41S)-8,21,41-tris[[diethyl(propan-2-yl)silyl]oxy]-1-methoxy-40-methoxycarbonyl-5,13-bis(4-methoxyphenyl)-19,20,22-trimethyl-17-oxo-4,6,12,14,18,43-hexaoxatetracyclo[37.3.1.13,7.111,15]pentatetraconta-23,25,27,29,31,33,35-heptaen-37-yl]oxy]oxan-3-yl] 1-O-[(3S,9S,10R,13R,14R,17R)-17-[(E,2R,5R)-5,6-dimethylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,9,11,12,14,15,16,17-decahydro-1H-cyclopenta[a]phenanthren-3-yl] butanedioate
• CAS: 1415683-21-4
• 化学式: C₁₃₃H₂₀₅NO₂₃Si₄
• 分子量: 2298.43
• InChiKey: ILWZKMVTPKXYKZ-PRLWBHHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  30.3
• 重原子数：
  161
• 可旋转键数：
  43
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  264
• 氢给体数：
  1
• 氢受体数：
  23

反应信息

• 作为产物：
  描述：

  methyl (1R,3S,7R,8R,11R,15R,19S,20S,21R,22S,23E,25E,27E,29E,31E,33E,35E,37R,39S,40S,41S)-8,21,41-tris[[diethyl(propan-2-yl)silyl]oxy]-37-[(2R,3S,4R,5S,6R)-5-[diethyl(propan-2-yl)silyl]oxy-3-hydroxy-6-methyl-4-[(2-phenylacetyl)amino]oxan-2-yl]oxy-1-methoxy-5,13-bis(4-methoxyphenyl)-19,20,22-trimethyl-17-oxo-4,6,12,14,18,43-hexaoxatetracyclo[37.3.1.13,7.111,15]pentatetraconta-23,25,27,29,31,33,35-heptaene-40-carboxylate 、 Ergosterol succinyl chloride 在 4-二甲氨基吡啶 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以14.5 mg的产率得到4-O-[(2R,3S,4R,5S,6R)-5-[diethyl(propan-2-yl)silyl]oxy-6-methyl-4-[(2-phenylacetyl)amino]-2-[[(1R,3S,7R,8R,11R,15R,19S,20S,21R,22S,23E,25E,27E,29E,31E,33E,35E,37R,39S,40S,41S)-8,21,41-tris[[diethyl(propan-2-yl)silyl]oxy]-1-methoxy-40-methoxycarbonyl-5,13-bis(4-methoxyphenyl)-19,20,22-trimethyl-17-oxo-4,6,12,14,18,43-hexaoxatetracyclo[37.3.1.13,7.111,15]pentatetraconta-23,25,27,29,31,33,35-heptaen-37-yl]oxy]oxan-3-yl] 1-O-[(3S,9S,10R,13R,14R,17R)-17-[(E,2R,5R)-5,6-dimethylhept-3-en-2-yl]-10,13-dimethyl-2,3,4,9,11,12,14,15,16,17-decahydro-1H-cyclopenta[a]phenanthren-3-yl] butanedioate
  参考文献：
  名称：

  [EN] ELECTRONIC TUNING OF SITE SELECTIVITY
  [FR] AJUSTEMENT ÉLECTRONIQUE DE SÉLECTIVITÉ DE SITE

  摘要：

  Amphotericin B的位选择性官能化已通过简单修改试剂的电子性质实现。 Hammett分析与将这一现象与Hammond假设联系起来是一致的：对更类似产物的过渡态进行电子调谐会增强试剂与其底物之间的区位区分相互作用。对酰基吡啶阳离子供体及其羧酸盐反离子的电子调谐进一步促进了位分歧官能化。对形成离子通道的天然产物Amphotericin B之一的许多羟基基团的一系列修饰已实现。

  公开号：

  WO2014059436A1

文献信息

• [EN] ELECTRONIC TUNING OF SITE SELECTIVITY<br/>[FR] AJUSTEMENT ÉLECTRONIQUE DE SÉLECTIVITÉ DE SITE
  申请人：UNIV ILLINOIS

  公开号：WO2014059436A1

  公开（公告）日：2014-04-17

  Site-selective functionalization of Amphotericin B has been achieved by simply modifying the electronic nature of the reagents. A Hammett analysis is consistent with linking of this phenomenon to the Hammond postulate: electronic tuning to a more product- like transition state amplifies site-discriminating interactions between a reagent and its substrate. Electronic tuning of both an acylpyridinium donor and its carboxylate counterion further promoted site-divergent functionalization. A range of modifications to one of the many hydroxyl groups appended to the ion channel-forming natural product amphotericin B was achieved.

  Amphotericin B的位选择性官能化已通过简单修改试剂的电子性质实现。 Hammett分析与将这一现象与Hammond假设联系起来是一致的：对更类似产物的过渡态进行电子调谐会增强试剂与其底物之间的区位区分相互作用。对酰基吡啶阳离子供体及其羧酸盐反离子的电子调谐进一步促进了位分歧官能化。对形成离子通道的天然产物Amphotericin B之一的许多羟基基团的一系列修饰已实现。