Structurally disfavoured pseudopeptidic macrocycles through anion templation

Bru, Miriam; Alfonso, Ignacio; Bolte, Michael; Burguete, M. Isabel; Luis, Santiago V.

doi:10.1039/c0cc01784a

Cited by 51 publications

(25 citation statements)

References 28 publications

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“…Within our ongoing research project devoted to the synthesis and the study of the properties of new pseudopeptidic compounds, [26] we envisioned the preparation of three-dimensional cage-like structures (Scheme 1). A simple and reasonable proposal to reach this aim should be the preparation of pseudopeptidic tris(amido amines) based on a tripodal central scaffold (black circle in Scheme 1) and three amino acidic units.…”

Section: Introductionmentioning

confidence: 99%

Tuning Chloride Binding, Encapsulation, and Transport by Peripheral Substitution of Pseudopeptidic Tripodal Small Cages

Martí

Rubio

Bolte

et al. 2012

Chemistry A European J

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A highly efficient synthesis of small pseudopeptidic cages from simple precursors has been achieved by the triple S(N)2 reaction between tripodal tris(amido amines) and several 1,3,5-tris(bromomethyl)benzene electrophiles. The success of the macrobicyclization strongly depends on the central triamine scaffold, which dictates the correct preorganization of the intermediates. The chloride binding properties of the protonated pseudopeptidic cages have been studied in the solid state (by X-ray diffraction) as well as in solution (by NMR spectroscopy and ESI-MS) and in the gas phase (by collision-induced dissociation (CID)-MS). The crystal structure of the HCl salts of several cages show a chloride partially or completely caged within the cavity of the macrobicycle. Both the amino acid side chain and the substitution at the aromatic tripodal ring have an effect on the chloride binding ability. The cages derived from the 1,3,5-benzene moiety show low affinity, whereas the triple substitution in the ring (either with Me or Et) increases the chloride binding by one order of magnitude. Besides, the cages derived from aliphatic amino acids display a stronger interaction than those derived from phenylalanine. The basis for the different mode of binding depending on the receptor structure is proposed according to the structural data (X-ray and NMR spectroscopy). Finally, the transport of the chloride anion through lipid bilayers has been studied for selected cages. Despite the important differences in the chloride binding, the transport properties are better correlated with the lipophilicity of the molecules. Therefore, the pseudopeptidic cages sharing the same binding motif for chloride rendered very different interaction and transport properties depending on the peripheral substitution.

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Section: Introductionmentioning

confidence: 99%

Tuning Chloride Binding, Encapsulation, and Transport by Peripheral Substitution of Pseudopeptidic Tripodal Small Cages

Martí

Rubio

Bolte

et al. 2012

Chemistry A European J

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“…The starting C 2 symmetric pseudopeptides 1-3 were synthesized as previously reported. [13][14][15] Compounds 1-3 were reacted in methanol with 1-ferrocenecarboxaldeyde at room temperature for four hours. Then, the reaction mixture was treated with NaBH 4 for two additional hours.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

Bisferrocenyl-functionalized pseudopeptides: access to separated ionic and electronic contributions for electrochemical anion sensing

et al. 2016

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“…Thus, by combining (R,R)-cyclohexane-1,2-diamine with l-amino acids (21), the systems are well preorganized to render the [2 + 2] macrocycle even in the absence of the tem plate [17,18]. Very interestingly, the anion-templation mechanism was also efficient in the mismatch combination of stereocenters, promoting the cycli zation of the molecules [19]. Very interestingly, the anion-templation mechanism was also efficient in the mismatch combination of stereocenters, promoting the cycli zation of the molecules [19].…”

Section: Pseudopeptidic Macrocyclesmentioning

confidence: 99%

Non‐covalent Interactions for the Preparation of Pseudopeptidic Synthetic Compounds and Materials

Solà

Alfonso

2016

Non‐covalent Interactions in the Synthesis and Design of New Compounds

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Structurally disfavoured pseudopeptidic macrocycles through anion templation

Abstract: An anionic dicarboxylate is able to template the formation of geometrically disfavoured macrocycles from a dynamic covalent mixture of open chain oligoimines.

Cited by 51 publications

References 28 publications

Tuning Chloride Binding, Encapsulation, and Transport by Peripheral Substitution of Pseudopeptidic Tripodal Small Cages

Tuning Chloride Binding, Encapsulation, and Transport by Peripheral Substitution of Pseudopeptidic Tripodal Small Cages

Bisferrocenyl-functionalized pseudopeptides: access to separated ionic and electronic contributions for electrochemical anion sensing

Non‐covalent Interactions for the Preparation of Pseudopeptidic Synthetic Compounds and Materials

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