Carbamic acid (2S,3S,4S)-3-hydroxy-5-oxo-4-(9-phenyl-9H-fluoren-9-ylamino)-tetrahydro-furan-2-ylmethyl ester | 152389-44-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: Carbamic acid (2S,3S,4S)-3-hydroxy-5-oxo-4-(9-phenyl-9H-fluoren-9-ylamino)-tetrahydro-furan-2-ylmethyl ester
• 英文别名: [(2S,3S,4S)-3-hydroxy-5-oxo-4-[(9-phenylfluoren-9-yl)amino]oxolan-2-yl]methyl carbamate
• CAS: 152389-44-1
• 化学式: C₂₅H₂₂N₂O₅
• 分子量: 430.46
• InChiKey: IIHHHGLKPUVKJN-FDFHNCONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  111
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  二碳酸二叔丁酯 、 Carbamic acid (2S,3S,4S)-3-hydroxy-5-oxo-4-(9-phenyl-9H-fluoren-9-ylamino)-tetrahydro-furan-2-ylmethyl ester 在 palladium on activated charcoal 氢气 作用下， 以 1,4-二氧六环 为溶剂， 反应 120.0h， 以97%的产率得到(2S,3S,4S)-2-amino>-4-(carbamoyloxy)-3-hydroxy-γ-butyrolactone
  参考文献：
  名称：

  Enantiomerically pure dimethyl (2S)-N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate as chiral educt. Chirospecific synthesis of (+)-5-O-carbamoylpolyoxamic acid and 3-alkylglutamates

  摘要：

  We report here a short and efficient synthesis (four steps, 78% overall yield) of dimethyl (2S)-N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate (1) in enantiomerically pure form from L-glutamic acid. The C-C double bond in 1 was introduced by selective selenenylation-oxidation of dimethyl N-(9-phenylfluoren-9-yl)glutamate. 1 did not undergo loss of enantiomeric purity when stored for several weeks at room temperature, thus demonstrating the ability of the 9-phenylfluoren-9-yl (Pf) group to protect the highly acidic chiral center of 1 from racemization. The alpha,beta-unsaturated carboxyl group of 1 was selectively reduced with DIBAL. Carbamoylation of the resulting alcohol, followed by OsO4-mediated hydroxylation of the double bond and deprotection afforded (+)-5-O-carbamoylpolyoxamic acid, a component of the polyoxin family of antifungal antibiotics (>40 % overall yield from glutamic acid). 1 underwent lithium dimethyl cuprate addition with complete retention of chiral integrity, albeit in a nonstereoselective fashion, to give 3-methylglutamates and 3-methylpyroglutamates.

  DOI：

  10.1021/jo00077a015
• 作为产物：
  描述：

  Methyl (2S)-2--5-hydroxy-3-pentenoate 在 吡啶 、 三乙烯二胺 、 ammonium hydroxide 、 四氧化锇 、 sodium hydrogensulfite 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.25h， 生成 Carbamic acid (2S,3S,4S)-3-hydroxy-5-oxo-4-(9-phenyl-9H-fluoren-9-ylamino)-tetrahydro-furan-2-ylmethyl ester
  参考文献：
  名称：

  Enantiomerically pure dimethyl (2S)-N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate as chiral educt. Chirospecific synthesis of (+)-5-O-carbamoylpolyoxamic acid and 3-alkylglutamates

  摘要：

  We report here a short and efficient synthesis (four steps, 78% overall yield) of dimethyl (2S)-N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate (1) in enantiomerically pure form from L-glutamic acid. The C-C double bond in 1 was introduced by selective selenenylation-oxidation of dimethyl N-(9-phenylfluoren-9-yl)glutamate. 1 did not undergo loss of enantiomeric purity when stored for several weeks at room temperature, thus demonstrating the ability of the 9-phenylfluoren-9-yl (Pf) group to protect the highly acidic chiral center of 1 from racemization. The alpha,beta-unsaturated carboxyl group of 1 was selectively reduced with DIBAL. Carbamoylation of the resulting alcohol, followed by OsO4-mediated hydroxylation of the double bond and deprotection afforded (+)-5-O-carbamoylpolyoxamic acid, a component of the polyoxin family of antifungal antibiotics (>40 % overall yield from glutamic acid). 1 underwent lithium dimethyl cuprate addition with complete retention of chiral integrity, albeit in a nonstereoselective fashion, to give 3-methylglutamates and 3-methylpyroglutamates.

  DOI：

  10.1021/jo00077a015