Conformational Analysis of β‐Lactam‐Containing Ferrocene Peptides

Kovač, Veronika; Radolović, Katarina; Habuš, Ivan; Siebler, Daniel; Heinze, Katja; Rapić, Vladimir

doi:10.1002/ejic.200800913

Cited by 25 publications

(11 citation statements)

References 64 publications

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“…Classical hydrogen bonds between electronegative elements are important in secondary structures of natural peptides as well as in catalysis. , However, also nonclassical hydrogen bonds such as XH···M and XH···HM play a significant role in modern chemistry, especially in organometallics with rather electron rich metal centers. − Organometallic peptides with conventional hydrogen bond forming ingredients, such as amino acids, − sugars, ureas, , and lactams, based on classical hydrogen bonds , have been extensively studied and exploited. Molecular wires, − redox-responsive foldamers, − optically switchable valence tautomers, , porphyrin tweezers, and anion sensors − have been devised from the combination of ferrocene and hydrogen bonds in organometallic systems.…”

Section: Introductionmentioning

confidence: 99%

Competitive NH···Ru/Fe Hydrogen Bonding in Ferrocenyl Ruthenocenyl Tosyl Hydrazone

et al. 2016

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A strong nonclassical NH•••Fe intramolecular hydrogen bond (IHB) is present in the literature-known diferrocenyl tosyl hydrazone (1). Here, we confirm by NMR and IR spectroscopy as well as by XRD methods that an analogous NH•••Ru IHB is present in the heavier homologue diruthenocenyl tosyl hydrazone (2). The NH•••Ru IHB in 2 is stronger than the NH•••Fe IHB in 1 by 6 kJ mol −1 , as determined by IR spectroscopy. Further, we probed the E/Z isomer directing abilities of NH•••M IHBs in the synthesis of the mixed metallocenyl compound ferrocenyl ruthenocenyl tosyl hydrazone (3). 3 is obtained as a mixture of the Z and E isomers (3a,b) with NH•••Ru and NH•••Fe IHBs, respectively. At 111 °C, 3a is preferred with an isomeric ratio of 10:1 (91% 3a). The formation of the isomeric mixture allows a direct comparison of the competitive NH•••Ru/Fe hydrogen bonding. The underlying reason for the 3a:3b ratio is of thermodynamic nature, rooted in the differences in strengths of the NH•••M IHBs of Fe and Ru. Thermal and photochemical approaches and protonation to the corresponding iminium/carbenium ions [H-3a] + /[H-3b] + were employed to overcome the barrier for the E → Z isomerization 3b → 3a, with concomitant switching of the NH•••M IHB.

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Section: Introductionmentioning

confidence: 99%

Competitive NH···Ru/Fe Hydrogen Bonding in Ferrocenyl Ruthenocenyl Tosyl Hydrazone

et al. 2016

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“…[13] By condensation of ferrocene acetyl chloride with 2-azetidinones substituted by a residue of alanine at the C3-position several b-lactam-containing ferrocene peptides have been prepared and their conformational properties were studied. [14] The macrocyclic bis-b-lactams 5, containing embedded Pd and Pt square-planar centers, were synthesized by the stepwise building of a bis-azetidinone system, having both rings tethered by an aliphatic chain, and the lactam nitrogen atom substituted by the terminal pyridine moieties 6. [15] Reaction of compounds 6 with cis-[M(dppe)(OTf) 2 ] (M= Pd, Pt, dppe = 1,2bis(diphenyl-phosphino)ethane, Tf = triflate) in the presence of NaOAc formed the diastereomerically pure metallic cavities 5 in essentially quantitative yields (Scheme 4).…”

Section: Incorporation Of the Metal In A Preformed B-lactammentioning

confidence: 99%

Bio‐Organometallic Derivatives of Antibacterial Drugs

Sierra

Casarrubios

Torre

2019

Chemistry A European J

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Overuse and misuse of antibacterial drugs has resulted in bacteria resistance and in an increase in mortality rates due to bacterial infections. Therefore, there is an imperative necessity of new antibacterial drugs. Bio-organometallic derivatives of antibacterial agents offer an opportunity to discover new active antibacterial drugs. These compounds are well-characterized products and, in several examples, their antibacterial activities have been studied. Both inhibition of the antibacterial activity and strong increase in the antibiotic activity of the parent drug have been found. The synthesis of the main classes of bio-organometallic derivatives of these drugs, as well as examples of the use of structure-activity relation&&Ok?&& (SAR) studies to increase the activity and to understand the mode of action of bio-organometallic antimicrobial peptides (BOAMPs) and platensimicyn bio-organometallic mimics is presented in this article.

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“…DFT calculations by Heinze and Rapić showed that the "Herrick" pattern is more stable than the "van Staveren" or "Xu" patterns. [14] P-and M-Helical conformations, which are interconvertible, based on a torsional twist about the Cp(centroid)-FeÀ Cp-(centroid) axis are present in the 1,n'-disubstituted ferrocene (Figure 5). [2] The introduction of the peptide chains, which have hydrogen bonding sites and chiral centers, into the ferrocene organometallic scaffold is expected to induce the helical chirality of the 1,n'-disubstituted ferrocene moiety by restriction of the torsional twist through the formation of intramolecular hydrogen bonds between the introduced chiral peptide chains.…”

Section: Introductionmentioning

confidence: 99%

Helical Chirality of Ferrocene Moieties in Cyclic Ferrocene‐Peptide Conjugates

Moriuchi

2021

Eur J Inorg Chem

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Ferrocene has been utilized as an organometallic scaffold for more than 25 years, serving as a central reverse-turn unit with the inter-ring spacing of about 3.3 Å. A variety of ferrocenepeptide conjugates have been designed to construct protein secondary structures and demonstrate the chirality organization via hydrogen bonding. In general, the helical chirality of ferrocene moieties in acyclic ferrocene-peptide conjugates is induced by the absolute configuration of the α-carbon atom of an amino acid adjacent to the ferrocene unit. Cyclization regulations restrict conformational flexibility of the peptide chains, inducing inversion of the helical chirality based on the reordering of the hydrogen bonding interactions. In this Minireview article, the helical chirality of ferrocene moieties in cyclic ferrocene-peptide conjugates is focused on. Controlled helical chirality of ferrocene moieties in a series of ferrocene-peptide conjugates by adjusting conformational flexibility of the peptide chains through cyclization regulations is introduced.

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Conformational Analysis of β‐Lactam‐Containing Ferrocene Peptides

Cited by 25 publications

References 64 publications

Competitive NH···Ru/Fe Hydrogen Bonding in Ferrocenyl Ruthenocenyl Tosyl Hydrazone

Competitive NH···Ru/Fe Hydrogen Bonding in Ferrocenyl Ruthenocenyl Tosyl Hydrazone

Bio‐Organometallic Derivatives of Antibacterial Drugs

Helical Chirality of Ferrocene Moieties in Cyclic Ferrocene‐Peptide Conjugates

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