dimethyl (4S,5S)-2-oxo-1-(9-phenylfluoren-9-yl)imidazolidine-4,5-dicarboxylate | 159518-45-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: dimethyl (4S,5S)-2-oxo-1-(9-phenylfluoren-9-yl)imidazolidine-4,5-dicarboxylate
• CAS: 159518-45-3
• 化学式: C₂₆H₂₂N₂O₅
• 分子量: 442.471
• InChiKey: NIMUNOWNHFGXTE-VXKWHMMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  84.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  甲基锂 、 dimethyl (4S,5S)-2-oxo-1-(9-phenylfluoren-9-yl)imidazolidine-4,5-dicarboxylate 以 四氢呋喃 、 乙醚 为溶剂， 生成 (4S,5S)-5-acetyl-2-oxo-3-(9'-phenylfluoren-9'-yl)imidazolidine-4-carboxylic acid methyl ester 、 (4S,5S)-5-(1-hydroxy-1-methylethyl)-2-oxo-3-(9'-phenylfluoren-9'-yl)imidazolidine-4-carboxylic acid methyl ester
  参考文献：
  名称：

  Enantiomerically Pure Highly Functionalized α-Amino Ketones from the Reaction of Chiral Cyclic N-(9-Phenylfluoren-9-yl) α-Amido Esters with Organolithium Reagents

  摘要：

  The reaction of methyl N-(9-phenylfluoren-9-yl)pyroglutamate with several organolithium reagents afforded the corresponding ketones in excellent yields and with complete retention of enantiomeric purity. The success of this transformation is due to the unusual stability of the tetrahedral intermediates 5, which stems from two factors: the electron-withdrawing effect of the amide nitrogen and the Lithium complexing ability of the fluorenyl ring of the 9-phenylfluoren-9-yl group, This ester-to-ketone transformation was also successfully applied to oxazolidinone 9 and imidazolidinone 20 and provided a ketone (21b) that was ultimately transformed inter the urea-lactam 26 which incorporates the bicyclic core of streptolidine lactam, a component of the streptrothricin antibiotics.

  DOI：

  10.1021/jo970277q
• 作为产物：
  描述：

  dimethyl (S)-N-(9-phenyl-9H-fluoren-9-yl)aspartate 在 palladium-barium carbonate 吡啶 、 4-二甲氨基吡啶 、 2,4,6-三异丙基苯磺酰叠氮化物 、 氢气 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， -78.0~70.0 ℃ 、101.33 kPa 条件下， 反应 2.35h， 生成 dimethyl (4S,5S)-2-oxo-1-(9-phenylfluoren-9-yl)imidazolidine-4,5-dicarboxylate
  参考文献：
  名称：

  On the Stereoselectivity of the Reaction of N-(9-Phenylfluoren-9-yl)aspartate Enolates with Electrophiles. Synthesis of Enantiomerically Pure 3-Hydroxy-, 3-Amino-, and 3-Hydroxy-3-methylaspartates

  摘要：

  We have developed efficient and stereoselective preparations of enantiomerically pure (3R)- and (3S)-N-Pf-3-hydroxy- and N-Pf-3-aminoaspartates by reaction of N-Pf-aspartate enolates with electrophilic hydroxylating or aminating reagents. The stereoselectivity of the hydroxylation and amination reactions was shown to be dependent on the structure of the enolate (which is strongly affected by the presence of strong metal complexing agents) and whether the electrophile is able to complex the enolate counterion in the transition state of the reaction. We have also developed a regioselective preparation of enantiomerically pure N-Pf-3-hydroxy-3-methylaspartates, albeit with only modest stereoselectivity.

  DOI：

  10.1021/jo00104a019

文献信息

• Enantiomerically Pure Highly Functionalized α-Amino Ketones from the Reaction of Chiral Cyclic <i>N</i>-(9-Phenylfluoren-9-yl) α-Amido Esters with Organolithium Reagents
  作者：Eduardo Fernández-Megía、José M. Iglesias-Pintos、F. Javier Sardina

  DOI：10.1021/jo970277q

  日期：1997.7.1

  The reaction of methyl N-(9-phenylfluoren-9-yl)pyroglutamate with several organolithium reagents afforded the corresponding ketones in excellent yields and with complete retention of enantiomeric purity. The success of this transformation is due to the unusual stability of the tetrahedral intermediates 5, which stems from two factors: the electron-withdrawing effect of the amide nitrogen and the Lithium complexing ability of the fluorenyl ring of the 9-phenylfluoren-9-yl group, This ester-to-ketone transformation was also successfully applied to oxazolidinone 9 and imidazolidinone 20 and provided a ketone (21b) that was ultimately transformed inter the urea-lactam 26 which incorporates the bicyclic core of streptolidine lactam, a component of the streptrothricin antibiotics.
• On the Stereoselectivity of the Reaction of N-(9-Phenylfluoren-9-yl)aspartate Enolates with Electrophiles. Synthesis of Enantiomerically Pure 3-Hydroxy-, 3-Amino-, and 3-Hydroxy-3-methylaspartates
  作者：Eduardo Fernandez-Megia、Manuel M. Paz、F. Javier Sardina

  DOI：10.1021/jo00104a019

  日期：1994.12

  We have developed efficient and stereoselective preparations of enantiomerically pure (3R)- and (3S)-N-Pf-3-hydroxy- and N-Pf-3-aminoaspartates by reaction of N-Pf-aspartate enolates with electrophilic hydroxylating or aminating reagents. The stereoselectivity of the hydroxylation and amination reactions was shown to be dependent on the structure of the enolate (which is strongly affected by the presence of strong metal complexing agents) and whether the electrophile is able to complex the enolate counterion in the transition state of the reaction. We have also developed a regioselective preparation of enantiomerically pure N-Pf-3-hydroxy-3-methylaspartates, albeit with only modest stereoselectivity.