(2S)-5-oxo-1-(9'-phenylfluoren-9'-yl)pyrrolidine-2-carboxylic acid methyl ester | 185121-30-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (2S)-5-oxo-1-(9'-phenylfluoren-9'-yl)pyrrolidine-2-carboxylic acid methyl ester
• 英文别名: methyl (2S)-5-oxo-1-(9-phenylfluoren-9-yl)pyrrolidine-2-carboxylate
• CAS: 185121-30-6
• 化学式: C₂₅H₂₁NO₃
• 分子量: 383.447
• InChiKey: RIILUFKGYRYLSP-QFIPXVFZSA-N

物化性质

• 沸点：
  556.3±50.0 °C(Predicted)
• 密度：
  1.284±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S)-5-oxo-1-(9'-phenylfluoren-9'-yl)pyrrolidine-2-carboxylic acid methyl ester 在 4-二甲氨基吡啶 、 L-Selectride 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 (S)-1-Benzenesulfonyl-pyrrolidine-2-carboxylic acid (S)-1-[(S)-5-oxo-1-(9-phenyl-9H-fluoren-9-yl)-pyrrolidin-2-yl]-ethyl 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：

  (S)-2-(9-Phenyl-9H-fluoren-9-ylamino)-pentanedioic acid 1-methyl ester 在 吡啶 、 对甲苯磺酰氯 作用下， 反应 10.0h， 以91%的产率得到(2S)-5-oxo-1-(9'-phenylfluoren-9'-yl)pyrrolidine-2-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

文献信息

• Rigid Dipeptide Mimetics:  Efficient Synthesis of Enantiopure Indolizidinone Amino Acids
  作者：Henry-Georges Lombart、William D. Lubell

  DOI：10.1021/jo961872f

  日期：1996.1.1

  An effective means to synthesize indolizidinone amino acids has been developed and furnishes all possible stereoisomers of these conformationally rigid mimetics of peptide secondary structures. Inexpensive glutamic acid was employed as chiral educt in a Claisen condensation/reductive amination/lactam cyclization sequence that furnished stereoselectively azabicyclo[3.4.0]alkane amino acid 1. Enantiopure (3S,6S,9S)- and (3R,6R,9R)-2-oxo-3-N-(BOC)amino-1-azabicyclo[4.3.0]nonane-9-carboxylic acids ((3S,6S,9S)- and (3R,6R,9R)-1) were respectively synthesized from L- and D-N-(PhF)glutamates 2 (PhF = 9-(9-phenylfluorenyl)). Slow addition of sodium bis(trimethylsilyl)amide to 2 provided good to excellent yields of beta-keto esters 3, which were subsequently hydrolyzed and decarboxylated to give symmetric alpha,omega-bis[N-(PhF)amino]azelate delta-ketones 5. Augmentation of hydrogen pressure increased diastereoselectivity in reductive aminations with 5 and afforded 5-alkylprolines 8 and 10. Lactam formation on exposure of 10 to triethylamine and N-protection with di-tert-butyl dicarbonate gave methyl 2-oxo-3-[N-(BOC)amino]-1-azabicyclo[4.3.0]nonane-9-carboxylate (12) which on C-terminal ester hydrolysis with hydroxide ion gave enantiopure [N-(BOC)amino]indolizidinone acid 1. Alternatively, hydride addition to ketone 5a gave symmetric alpha,omega-bis[N-(PhF)amino]azelate delta-alcohol 7a, which upon mesylation, and intramolecular S(N)2 displacement by the PhF amine gave specifically cis-5-alkylproline 15 that was similarly converted to (3S,6S,9S)-1. In addition, epimerization of the C-9 stereocenter of (3S,6S,9S)-[N-(BOC)amino]-indolizidinone methyl ester 12 with NaN(SiMe(3))(2) and ester hydrolysis gave (3S,6S,9R)-indolizidinone amino acid (3S,6S,9R)-1. By providing efficient methodology for synthesizing all of the possible stereoisomers of enantiopure indolizidinone amino acid 1, our route is specifically designed to enhance the general use of these peptide mimetics in the exploration of conformation-activity relationships of various biologically active peptides.
• 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.