L-丝氨酸,N-[(9H-芴-9-基甲氧基)羰基]-L-缬氨酰-,苯基甲基酯 | 186023-39-2

• 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
• 中文名称: L-丝氨酸,N-[(9H-芴-9-基甲氧基)羰基]-L-缬氨酰-,苯基甲基酯
• 中文别名: L-丝氨酸,N-[(9H-芴-9-基甲氧基)羰基]-L-缬氨酰-,苯基甲基酯
• 英文名称: Fmoc-Val-Ser-OBn
• 英文别名: benzyl (2S)-2-[[(2S)-2-(9H-fluoren-9-ylmethoxycarbonylamino)-3-methylbutanoyl]amino]-3-hydroxypropanoate
• CAS: 186023-39-2
• 化学式: C₃₀H₃₂N₂O₆
• 分子量: 516.594
• InChiKey: ZXFRBAMNTOYCJN-SVBPBHIXSA-N

物化性质

• 沸点：
  756.5±60.0 °C(Predicted)
• 密度：
  1.243±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  114
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  L-丝氨酸,N-[(9H-芴-9-基甲氧基)羰基]-L-缬氨酰-,苯基甲基酯 在 palladium on activated charcoal 氢气 、 4-甲基苯磺酸吡啶 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 15.0h， 生成 (4S)-3-[(2S)-2-[[芴甲氧羰基]氨基]-3-甲基-1-氧代丁基]-2,2-二甲基-4-恶唑烷羧酸
  参考文献：
  名称：

  Pseudo-Prolines as a Molecular Hinge:  Reversible Induction of cis Amide Bonds into Peptide Backbones

  摘要：

  Serine, threonine-derived (4S)-oxazolidine-4-carboxylic acid, and cysteine-derived (4R)-thiazolidinecarboxylic acid, denoted pseudo-proline (Xaa[Psi(R1,R2)pro]), serve as structure disrupting, solubilizing building blocks in peptide synthesis. Variation of the 2-C substituents within the heterocyclic system results in different physicochemical and conformational properties. NMR studies of a series of pseudo-proline (Psi Pro)-containing peptides reveal a pronounced effect of the 2-C substituents upon the cis to trans ratio of the adjacent amide bond in solution. 2-C unsubstituted systems show a preference similar to that of the proline residue for the trans form, whereas 2,2-dimethylated derivatives adopt the cis amide conformation in high content. For 2-monosubstituted Psi Pro, the cis-trans distribution depends on the 2-C chirality. For the 2-(S)-diastereoisomer, both forms are similarly populated in solution, whereas the 2-(R)-epimer adopts preferentially the trans form. The results are supported by conformational energy calculations and suggest that, by tailoring the degree of substitution, pseudo-prolines may serve as a temporary proline mimetic or as a hinge in peptide backbones.

  DOI：

  10.1021/ja962780a
• 作为产物：
  描述：

  benzyl (4S)-3-((((9H-fluoren-9-yl)methoxy)carbonyl)-L-valyl)-2-(2-hydroxyphenyl)oxazolidine-4-carboxylate 在 三异丙基硅烷 、 水 、 三氟乙酸 作用下， 反应 0.08h， 生成 L-丝氨酸,N-[(9H-芴-9-基甲氧基)羰基]-L-缬氨酰-,苯基甲基酯
  参考文献：
  名称：

  Salicylaldehyde Ester-Induced Chemoselective Peptide Ligations: Enabling Generation of Natural Peptidic Linkages at the Serine/Threonine Sites

  摘要：

  A serine/threonine-based chemoselective ligation method is described. It uses an O-salicylaldehyde ester at the C-terminus, reacting with N-terminal serine or threonine to realize peptide ligations. The utility of the O-salicylaldehyde ester enables the rapid coupling reaction and the production of an N,O-benzylidene acetal intermediate, which is readily converted into natural peptidic linkages (Xaa-Ser/Thr) at the ligation site.

  DOI：

  10.1021/ol1003109

文献信息

• Stereocontrol during the formation of 2-C mono-arylated pseudo-prolines by aromatic stacking interaction
  作者：Michael Keller、Christian Lehmann、Manfred Mutter

  DOI：10.1016/s0040-4020(98)01039-4

  日期：1999.1

  When treated with anisaldehyde dimethylacetal the O-benzyl ester protected dipeptide Fmoc-NMeIle-Thr-OBzl (2, cf. Scheme 3), cyclizes to the 2-C(S) epimer 3b assigned by NMR spectroscopy to chirality (R) at the 2-C position of the resulting substituted 1,3-oxazolidine (Psi Pro) unit, while in the acetalization of the corresponding O-methylester Fmoc-NMeIle-Thr-OMe (6),the 2-C(S) epimer 7a is predominantly formed stereoselectively and in quantitative yield. The course of the reaction can be rationalized by aromatic stacking interactions involving the benzyl ester and aryl ether groups in a transition state close to a product structure of(R) chirality, whereas the lack of such interactions in the case of the methyl ester can be used to direct the acetalization towards the 2-C(S) epimer. (C) 1998 Elsevier Science Ltd. All rights reserved.
• The total synthesis of bistratamides F–I
  作者：Shu-Li You、Jeffery W. Kelly

  DOI：10.1016/j.tet.2004.10.024

  日期：2005.1

  The total synthesis of bistratamides F-I (2-5) have been achieved in overall yields of 3, 10, 13, and 27%, respectively. The thiazole substructure was prepared utilizing a MnO2 oxidation of a thiazoline, synthesized from a Val-Cys dipeptide using bis(triphenyl)oxodiphosphonium trifluoromethanesulfonate. The serine-based oxazole substructure was prepared from a Val-Ser dipeptide using literature methods. The threonine-derived oxazole substructure was synthesized from a ketoamide dipeptide using the bisphosphonium salt employed for thiazoline preparation. Most of the amide bonds were formed using HBTU and HOBt in the presence of DIEA. The final macrocyclization step was accomplished efficiently by PyBOP and DMAP in all cases. (C) 2004 Elsevier Ltd. All rights reserved.