Dimethyl N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate | 152389-36-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: Dimethyl N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate
• 英文别名: dimethyl (E,4S)-4-[(9-phenylfluoren-9-yl)amino]pent-2-enedioate
• CAS: 152389-36-1
• 化学式: C₂₆H₂₃NO₄
• 分子量: 413.473
• InChiKey: YMRQQBHKJAOXRK-OFYULWLWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Dimethyl N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 以86%的产率得到Methyl (2S)-2--5-hydroxy-3-pentenoate
  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：

  (S)-2-(9-Phenyl-9H-fluoren-9-ylamino)-pentanedioic acid dimethyl ester 在 potassium phosphate 、 双(三甲基硅烷基)氨基钾 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 Dimethyl N-(9-phenylfluoren-9-yl)-3,4-didehydroglutamate
  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

文献信息

• 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
  作者：Manuel M. Paz、F. Javier Sardina

  DOI：10.1021/jo00077a015

  日期：1993.12

  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.