(1S,3S,6S,7S,8S,9R)-3-azido-7-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methyl]-9-phenylmethoxy-5-azatricyclo[6.3.1.01,5]dodecan-4-one | 1395688-56-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (1S,3S,6S,7S,8S,9R)-3-azido-7-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methyl]-9-phenylmethoxy-5-azatricyclo[6.3.1.01,5]dodecan-4-one
• CAS: 1395688-56-8
• 化学式: C₃₂H₄₄N₄O₄Si
• 分子量: 576.811
• InChiKey: MOVMFSJLHODZTM-QMPCPGQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.05
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  62.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1S,3S,6S,7S,8S,9R)-3-azido-7-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methyl]-9-phenylmethoxy-5-azatricyclo[6.3.1.01,5]dodecan-4-one 在 lithium aluminium tetrahydride 、 palladium 10% on activated carbon 、 氢气 、 三乙胺 、 三(4-氯苯基)膦 、 DIAD 作用下， 以 四氢呋喃 为溶剂， 20.0~60.0 ℃ 、101.33 kPa 条件下， 反应 17.0h， 生成 Phosphoric acid dibenzyl ester (1S,3S,6S,7S,8R,9S)-7-hydroxy-6-(4-methoxy-benzyl)-3-methylamino-5-aza-tricyclo[6.3.1.01,5]dodec-9-yl ester
  参考文献：
  名称：

  Enantioselective Total Syntheses of (−)-FR901483 and (+)-8-epi-FR901483

  摘要：

  The enantioselective total syntheses of the potent immunosuppressant FR901483 (1) and its 8-epimer (47) have been accomplished. Our approach features the use of building block 6 as the chiron, the application of the one-pot amide reductive bis-alkylation method to construct the chiral aza-quaternary center (dr = 9:1), regio- and diaster-eoselective intramolecular aldol reaction to build the bridged ring, and RCM to form the 3-pyrrolin-2-one ring.

  DOI：

  10.1021/jo302362b
• 作为产物：
  描述：

  (1S,5S,6R)-2-allyl-1-vinyl-2-azaspiro[bicyclo[3.3.1]nonane-4,2'-[1,3]dioxolan]-6-ol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 titanium(IV) isopropylate 、 盐酸 、 六甲基磷酰三胺 、 四(三苯基膦)钯 、 samarium diiodide 、 palladium 10% on activated carbon 、 氢气 、 四丁基碘化铵 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 为溶剂， -78.0~85.0 ℃ 、101.33 kPa 条件下， 反应 52.58h， 生成 (1S,3S,6S,7S,8S,9R)-3-azido-7-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methyl]-9-phenylmethoxy-5-azatricyclo[6.3.1.01,5]dodecan-4-one 、 (1S,3R,6S,7S,8S,9R)-3-azido-7-[tert-butyl(dimethyl)silyl]oxy-6-[(4-methoxyphenyl)methyl]-9-phenylmethoxy-5-azatricyclo[6.3.1.01,5]dodecan-4-one
  参考文献：
  名称：

  Enantioselective Total Syntheses of (−)-FR901483 and (+)-8-epi-FR901483

  摘要：

  The enantioselective total syntheses of the potent immunosuppressant FR901483 (1) and its 8-epimer (47) have been accomplished. Our approach features the use of building block 6 as the chiron, the application of the one-pot amide reductive bis-alkylation method to construct the chiral aza-quaternary center (dr = 9:1), regio- and diaster-eoselective intramolecular aldol reaction to build the bridged ring, and RCM to form the 3-pyrrolin-2-one ring.

  DOI：

  10.1021/jo302362b

文献信息

• Enantioselective Total Syntheses of (−)-FR901483 and (+)-8-<i>epi</i>-FR901483
  作者：Hao-Hua Huo、Xiao-Er Xia、Hong-Kui Zhang、Pei-Qiang Huang

  DOI：10.1021/jo302362b

  日期：2013.1.18

  The enantioselective total syntheses of the potent immunosuppressant FR901483 (1) and its 8-epimer (47) have been accomplished. Our approach features the use of building block 6 as the chiron, the application of the one-pot amide reductive bis-alkylation method to construct the chiral aza-quaternary center (dr = 9:1), regio- and diaster-eoselective intramolecular aldol reaction to build the bridged ring, and RCM to form the 3-pyrrolin-2-one ring.