L-N-(9-(9-phenylfluorenyl))glutamic acid γ-methylester | 119595-72-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: L-N-(9-(9-phenylfluorenyl))glutamic acid γ-methylester
• 英文别名: N-(9-(9-phenylfluorenyl))glutamic acid γ-methyl ester；γ-Methyl N-(9-(9-phenylfluorenyl))-L-glutamate；(2S)-γ-methyl N-(PhF)-glutamate；PhFl-Glu(OMe)-OH；(2S)-5-methoxy-5-oxo-2-[(9-phenylfluoren-9-yl)amino]pentanoic acid
• CAS: 119595-72-1
• 化学式: C₂₅H₂₃NO₄
• 分子量: 401.462
• InChiKey: ISIMQGJOWMXCEC-QFIPXVFZSA-N

物化性质

• 熔点：
  142-143 °C
• 沸点：
  601.7±55.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  75.6
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  L-N-(9-(9-phenylfluorenyl))glutamic acid γ-methylester 在 lithium aluminium tetrahydride 、 四溴化碳 、 双(三甲基硅烷基)氨基钾 、 N,N-二异丙基乙胺 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 43.0h， 生成 (4S)-4-甲基-l-脯氨酸
  参考文献：
  名称：

  Synthesis of 4-substituted prolines as conformationally constrained amino acid analogs

  摘要：

  DOI：

  10.1021/jo00269a022
• 作为产物：
  描述：

  L-谷氨酸-5-甲酯 在 lead(II) nitrate 、 三乙胺 作用下， 以 氯仿 为溶剂， 反应 89.0h， 生成 L-N-(9-(9-phenylfluorenyl))glutamic acid γ-methylester
  参考文献：
  名称：

  Synthesis of 4-substituted prolines as conformationally constrained amino acid analogs

  摘要：

  DOI：

  10.1021/jo00269a022

文献信息

• Acid-Labile Protecting Groups for the Synthesis of Lipidated Peptides
  作者：Dieter Kadereit、Patrick Deck、Ines Heinemann、Herbert Waldmann

  DOI：10.1002/1521-3765(20010316)7:6<1184::aid-chem1184>3.0.co;2-5

  日期：2001.3.16

  Lipidated peptides and their neolipoprotein derivatives are efficient tools for the investigation of biological processes in molecular detail. These compounds are often acid- and base-labile, and their synthesis requires the use of a combination of blocking groups that can be removed under very mild conditions. In this article we demonstrate that the Boc urethane and different trityl-type protecting groups

  脂质肽及其新脂蛋白衍生物是用于详细研究分子生物学过程的有效工具。这些化合物通常对酸和碱不稳定，并且它们的合成需要使用可以在非常温和的条件下除去的保护基团的组合。在本文中，我们证明了Boc氨基甲酸酯和不同的三苯甲基型保护基可以在足够温和以适应脂肽合成需求的酸性条件下选择性裂解。因此，在二甲基吡啶存在的情况下，Boc基团被TMS三氟甲磺酸酯裂解，在三乙基硅烷作为阳离子清除剂的情况下，在二氯甲烷中用1％TFA除去甲基三苯甲基（Mtt）和甲氧基三苯甲基（Mmt）基团。
• Synthesis of (S)-2-Amino-3-(3-tert-butyl-5-oxo-2H-isoxazol-4-yl)propionic Acid
  作者：Mohamed Atfani、William D. Lubell

  DOI：10.1021/jo00115a039

  日期：1995.5

  An efficient method for synthesizing enantiopure isoxazole amino acids has been developed. (2S)-2-Amino-3-(3-tert-tert-butyl-5-oxo-2H-isoxazol-4-yl) propionic acid (1) was synthesized in three steps from L-gamma-methyl N-(9-(9-phenylfluorenyl))glutamate (2) in 46% overall yield. Acylation of the dianion of 2 with pivaloyl chloride provides beta-keto ester 3 in 75% yield after chromatography. (2S)-2-[N-(9-(9-phenylfluorenyl))amino]-3 -(3-tert-butyl-5-oxo-2H-isoxazol-4-yl)propionic acid (4) was isolated as a white crystalline solid from the reaction of 3 with hydroxylamine under basic conditions followed by exposure to HCl. The crystal structure of 4 confirmed the presence of a 3-tert-butyl-4-isoxazol-5(2H)-one. Title compound 1 was obtained by removal of the PhFl protecting group of 4 using either trifluoroacetic acid in CH2Cl2 or lithium in liquid ammonia. Alkylation of 4 with iodomethane provided a mixture containing (2S,4S)-methyl 2-[N-(9-(9-phenylfluorenyl))amino]-3-(3 -tert-butyl-4-methyl-5-oxo-4H-isoxazol-4-yl)propionate (5) and (2S)-methyl 2-[N-(9-(9-phenylfluorenyl))amino]-3-(2-methyl-3-tert-butyl-5-oxo-2H-isoxazol-4-yl)propionate (6). Single crystal X-ray analyses of the structures of 4-6 provide insight into the mechanism of alkylation as well as the configurational stability of N-(9-(9-phenylfluorenyl))amino carbonyl compounds.
• Mulzer, Johann; Schroeder, Fridtjof; Lobbia, Alessandro, Angewandte Chemie, 1994, vol. 106, # 17, p. 1813 - 1815
  作者：Mulzer, Johann、Schroeder, Fridtjof、Lobbia, Alessandro、Buschmann, Juergen、Luger, Peter

  DOI：——

  日期：——
• 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.
• KOSKINEN, ARI M. P.;RAPOPORT, HENRY, J. ORG. CHEM., 54,(1989) N, C. 1859-1866
  作者：KOSKINEN, ARI M. P.、RAPOPORT, HENRY

  DOI：——

  日期：——