Unexpected Stability of the Urea cis−trans Isomer in Urea-Containing Model Pseudopeptides

Semetey, Vincent; Hemmerlin, Christine; Didierjean, Claude; Schaffner, Arnaud‐Pierre; Giner, Ana Gimenez; Aubry, A.; Briand, Jean‐Paul; Marraud, Michel; Guichard, Gilles

doi:10.1021/ol0166552

Cited by 49 publications

(37 citation statements)

References 13 publications

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“…The computed IR frequencies are comparable to the experimental ones. 46 The calculated HOMO−LUMO gap is 9 eV, similar to that for molecules in M1 and M2. Tuning of the acceptor end polarized the structure, which set a similar trend for charge separation at the donor and acceptor sites as that in the models mentioned above.…”

Section: Model 2 (M2)supporting

confidence: 63%

Computational Studies on Structural, Excitation, and Charge-Transfer Properties of Ureidopeptidomimetics

2016

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Peptides with ureido group enclosing backbones are considered peptidomimetics and are known for their higher stabilities, biocompatibilities, antibiotic, inhibitor, and charge-transduction activities. These peptidomimetics have some unique applications, which are quite different from those of natural peptides. Hence, it is imperative to appreciate their properties at a microscopic level. In this regard, this work outlines, in detail, the charge transfer (CT) properties, holemigration dynamics, and electronic structures of various experimentally comprehended ureidopeptidomimetic models using density functional theory (DFT). Time-dependent DFT and complete active space self-consistent field computations on basic models provide the necessary evidence for the viability of CT from the end enfolding the ureido group to the other end with a carboxylate entity. This donor-to-acceptor CT has been reflected in excitation studies, in which the higher intensity band corresponds to CT from the π orbital of the ureido group to the π* orbital of the carboxylate entity. Further, hole-migration studies have shown that charge can evolve from the ureido end, whereas the hole generated at the carboxylate end does not migrate. However, hole migration has been reported to occur from both ends (amino and carboxylate ends) in glycine oligopeptides, and our studies show that the ability to transfer and migrate charge can be tuned by modifying the donor and acceptor functional groups in both the neutral and cationic charge states. We have analyzed the possibility of hole migration following ionization using DFT-based wave-packet propagation and found its occurrence on a ∼2−5 fs time scale, which reflects the charge-transduction ability of peptidomimetics.

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Section: Model 2 (M2)supporting

confidence: 63%

Computational Studies on Structural, Excitation, and Charge-Transfer Properties of Ureidopeptidomimetics

2016

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“…H-bonding distances in these compounds are longer than that found in compound 1 (see below), whereas those found in the butyrate are 2.916 (5) and 2.918 (5) A. For the diglycine system a H-bonding distance of 2.916 (7) A was reported [15] Guichard and coworkers [16] reported H-bonded distances ranging from 2.83 to 3.27 A for a leucine-urea derivative. The Hbonding interactions in this urea are fundamentally different.…”

Section: Resultsmentioning

confidence: 81%

Electronic communication through the ureylene bridge: spectroscopy, structure and electrochemistry of dimethyl 1′,1′-ureylenedi(1-ferrocenecarboxylate)

Mahmoud

Long

Schatte

et al. 2004

Journal of Organometallic Chemistry

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“…The succinimidyl carbamate (OSu) derivatives (S)-6 or (R)-6 (Boc-(S or R)-BAC-OSu), (S)-7 and (S)-8 (Boc-(S)-APC-OSu and Boc-(S)-APPC-OSu), precursors of oligoureas, were prepared from Boc-(S or R)-ABOC-OH, Boc-(S)-b 3 -hAla-OH, and Boc-(S)-b 3 -hPhe-OH, respectively. [10,12] As previously reported for BAC homo-oligoureas, [10] Nbenzhydryl-glycolamide ester (OBg ester) was introduced at the C-terminal part of the oligoureas as a b-Ala-OBg residue and a 4-bromophenyl group was introduced through its isocyanate derivative for capping the oligourea N-terminus.…”

Section: Resultsmentioning

confidence: 99%

Mixed Oligoureas Based on Constrained Bicyclic and Acyclic β‐Amino Acids Derivatives: On the Significance of the Subunit Configuration for Folding

André

Legrand

Moulat

et al. 2013

Chemistry A European J

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The combination of a non-functionalized constrained bicyclo[2.2.2]octane motif along with urea linkages allowed the formation of a highly rigid 2.5(12/14) helical system both in solution and the solid state. In this work, we aimed at developing stable and functionalized systems as promising materials for biological applications in investigating the impact of this constrained motif and its configuration on homo and heterochiral mixed-oligourea helix formation. Di-, tetra-, hexa-, and octa-oligoureas alternating the highly constrained bicyclic motif of (R) or (S) configuration with acyclic (S)-β(3)-amino acid derivatives were constructed. Circular dichroism (CD), NMR experiments, and the X-ray crystal structure of the octamer unequivocally proved that the alternating heterochiral R/S sequences form a stable left-handed 2.5-helix in contrast to the mixed (S/S)-oligoureas, which did not adopt any defined secondary structure. We observed that the (-)-synclinal conformation around the C(α)-C(β) bond of the acyclic residues, although sterically less favorable than the (+)-synclinal conformation, was imposed by the (R)-bicyclic amino carbamoyl (BAC) residue. This highlighted the strong ability of the BAC residue to drive helical folding in heterochiral compounds. The role of the stereochemistry of the BAC unit was assessed and a model was proposed to explain the misfolding of the S/S sequences.

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Unexpected Stability of the Urea cis−trans Isomer in Urea-Containing Model Pseudopeptides

Cited by 49 publications

References 13 publications

Computational Studies on Structural, Excitation, and Charge-Transfer Properties of Ureidopeptidomimetics

Computational Studies on Structural, Excitation, and Charge-Transfer Properties of Ureidopeptidomimetics

Electronic communication through the ureylene bridge: spectroscopy, structure and electrochemistry of dimethyl 1′,1′-ureylenedi(1-ferrocenecarboxylate)

Mixed Oligoureas Based on Constrained Bicyclic and Acyclic β‐Amino Acids Derivatives: On the Significance of the Subunit Configuration for Folding

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