dimethyl (4S,5S)-2-oxo-3-(9-phenylfluoren-9-yl)-1,3-oxazolidine-4,5-dicarboxylate | 144331-17-9

• 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-3-(9-phenylfluoren-9-yl)-1,3-oxazolidine-4,5-dicarboxylate
• CAS: 144331-17-9
• 化学式: C₂₆H₂₁NO₆
• 分子量: 443.456
• InChiKey: RHYMZLGONFUXMH-VXKWHMMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 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：
  82.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲基锂 、 dimethyl (4S,5S)-2-oxo-3-(9-phenylfluoren-9-yl)-1,3-oxazolidine-4,5-dicarboxylate 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.5h， 以99%的产率得到(4S,5S)-5-acetyl-2-oxo-3-(9'-phenylfluoren-9'-yl)oxazolidine-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：

  (2S,3S)-Dimethyl N-(9'-phenylfluoren-9'-yl)-3-hydroxyaspartate 、 氯甲酸三氯甲酯 在 吡啶 、 4-二甲氨基吡啶 作用下， 生成 dimethyl (4S,5S)-2-oxo-3-(9-phenylfluoren-9-yl)-1,3-oxazolidine-4,5-dicarboxylate
  参考文献：
  名称：

  天冬氨酸二酯烯酸酯的羟基化立体立体手性合成（3 R）和（3 S）3-羟基天冬氨酸

  摘要：

  描述了通过天冬氨酸烯醇酸酯的羟基化来合成N-（9-苯基芴基）-3-羟基天冬氨酸的手性和立体发散的方法。新产生的手性中心的立体化学由烯醇盐抗衡离子的性质和溶剂的配体配位能力控制。

  DOI：

  10.1016/s0040-4039(00)61333-3

文献信息

• 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.
• 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.
• A stereodivergent chirospecific synthesis of (3R) and (3S) 3-hydroxyaspartates by hydroxylation of aspartate diester enolates
  作者：F.Javier Sardina、Manuel M. Paz、Eduardo Fernández-Megía、Richard F. de Boer、M.Pilar Alvarez

  DOI：10.1016/s0040-4039(00)61333-3

  日期：1992.8

  A chirospecific and stereodivergent synthesis of N-(9-phenylfluorenyl)-3-hydroxyaspartates by hydroxylation of aspartate enolates is described. The stereochemistry of the newly created chiral center is controlled by the nature of the enolate counterion and the ligand coordinating ability of the solvents.

  描述了通过天冬氨酸烯醇酸酯的羟基化来合成N-（9-苯基芴基）-3-羟基天冬氨酸的手性和立体发散的方法。新产生的手性中心的立体化学由烯醇盐抗衡离子的性质和溶剂的配体配位能力控制。