[Fe(C5H4CO-β-Ala-OMe)2] | 956004-24-3

• 英文名称: [Fe(C5H4CO-β-Ala-OMe)2]
• CAS: 956004-24-3
• 化学式: C₂₀H₂₄FeN₂O₆
• 分子量: 444.267
• InChiKey: ODHNINWZVFKSHC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  1,1'-bisferrocenedicarboxylic acid 、 3-氨基丙酸甲酯盐酸盐 、 L-苯丙氨酸甲酯盐酸盐 在 (o-benzotriazol-N,N,N,N-tetramethyluronium)PF₆ 、 1-hydroxybenzotriazole 、 diisopropylethylamine 作用下， 以 二氯甲烷 为溶剂， 以22%的产率得到[Fe(C5H4CO-Phe-OMe)(C5H4CO-β-Ala-OMe)]
  参考文献：
  名称：

  A systematic evaluation of different hydrogen bonding patterns in unsymmetrical 1,n′-disubstituted ferrocenoyl peptides

  摘要：

  The synthesis and spectroscopic characterization of 21 1,1'-disubstituted ferrocenoyl peptides of the general formula [Fe(C5H4-CO-Aa1-OR) (C5H4-CO-Aa2-OR')] is reported, with Aa1 and Aa2 being different amino acids. The one-pot synthesis from activated ferrocene-1,1'-dicarboxylic acid and two different amino acid esters gives the unsymmetrical ferrocenoyl peptides in yields between 27% and 42%, which can be easily separated from their symmetrical byproducts by column chromatography. All new compounds are comprehensively characterized by mass spectrometry (El and FAB, including high-resolution EI-MS), H-1 and C-13 NMR, and UV/Vis spectroscopy. CD spectroscopy in conjunction with H-1 NMR is used to elucidate the solution structures. Using the achiral glycine (Gly) as Aa1 permits to determine qualitatively the structure-determining influence of the different amino acids Aa2. Helically chiral structures in ferrocene amino acids in this study are stabilized by hydrogen bonds. If one hydrogen bond partner is systematically moved away by the introduction of methylene groups, then indeed the strength of the hydrogen bond decreases as indicated by 1 H NMR chemical shifts of the amide protons and the strength of characteristic CD bands. As proline (Pro) is the only naturally accuring secondary amino acid it cannot contribute any amide proton to intra-strand hydrogen bonding. DFT calculations on the compound [Fe(C5H4-CO-GlyOMe)(C5H4-CO-Pro-OMe)] with one achiral and one secondary amino acid were therefore performed to quantify the more subtle influence of the relative orientations of the ferrocene carbonyl groups and the cis-/trans-conformation of both amide bonds. Not unexpectedly, the conformations with both amide bonds in cis orientation are highest in energy. Surprisingly, the calculations suggest the presence of a low-energy conformation with a non-classical hydrogen bond between the proline ester carbonyl oxygen and a glycine Ha atom. However, a second conformation with no apparent intra-strand contacts but optimal positioning of all relevant groups is similar in energy. Although two conformations were observed in solution for this compound, the experimental data did not permit to assign those two conformations. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2008.01.050