Helically chiral ferrocene peptides containing 1′ -aminoferrocene-1-carboxylic acid subunits as turn inducers

Lidija Barišić, Mojca Čakić, Khaled Mahmoud, You Nian Liu, Heinz Bernhard Kraatz, Hans Pritzkow, Srećko I. Kirin, Nils Metzler-Nolte, Vladimir Rapić

Research output: Contribution to journalArticle

120 Citations (Scopus)

Abstract

We present a detailed structural study of peptide derivatives of 1′-aminoferrocene-1-carboxylic acid (ferrocene amino acid, Fca), one of the simplest organometallic amino acids. Fca was incorporated into di- to pentapeptides with D- and L-alanine residues attached to either the carboxy or amino group, or to both. Crystallographic and spectroscopic studies (circular dicroism (CD), IR, and NMR) of about two dozen compounds were used to gain a detailed insight into their structures in the solid state as well as in solution. Four derivatives were characterized by single-crystal X-ray analysis, namely Boc-Fca-Ala-OMe (16), Boc-Fca-D-Ala-OMe (17), Boc-Fca-β-Ala-OMe (18), and Boc-Ala-Fca-Ala-Ala-OMe (21) (Boc = tert-butyloxycarbamyl). CD spectroscopy is an extremely useful tool to elucidate the hel ical chirality of the metallocene core. Unlike in all other known ferrocene peptides, the helical chirality of the ferrocene is governed solely by the chirality of the amino acid attached to the N terminus of Fca. Depending on the degree of substitution of both cyclopentadiene (Cp) rings, different hydrogen-bonding patterns are realized. 1H NMR and IR spectroscopy, together with the results from X-ray crystallography, give detailed information regarding not only the hydrogen-bonding patterns of the compounds, but also the equilibria between different conformers in solution. Differences in chemical shifts of NH protons in dimethyl sulf oxide ([D6]DMSO) and CDCl3, that is, the variation ratio (vr), is used for the first time as a measure of the hydrogen-bonding strength of individual CO⋯HN bonds in ferrocenoyl peptides. In dipeptides with one intramolecular hydrogen bond between the pendant chains, for example, in dipeptide 16, an equilibrium between hydrogenbonded and open forms is observed, as testified by a vr value of around 0.5. Higher peptides, such as tetrapeptide 21, are able to' form two intramolecular hydrogen bonds stabilizing one single conformation in CDCl 3 solution (vr ≈0). Due to the low barrier of Cp-ring rotation, new and unnatural hydrogen-bonding patterns are emerging. The systematic work described herein lays a solid foundation for the rational design of metallocene peptides with unusual structures and properties.

Original languageEnglish
Pages (from-to)4965-4980
Number of pages16
JournalChemistry - A European Journal
Volume12
Issue number19
DOIs
Publication statusPublished - 23 Jun 2006
Externally publishedYes

Fingerprint

Amino Acids
Peptides
Hydrogen bonds
Hydrogen Bonding
Chirality
Cyclopentanes
Dipeptides
Hydrogen
Derivatives
1'-aminoferrocene-1-carboxylic acid
ferrocene
X ray crystallography
X Ray Crystallography
X ray analysis
Chemical shift
Organometallics
Dimethyl Sulfoxide
Alanine
Oxides
Nuclear magnetic resonance spectroscopy

Keywords

  • Amino acids
  • Bioorganometallic chemistry
  • Ferrocene
  • Hydrogen bonds
  • Peptides

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Helically chiral ferrocene peptides containing 1′ -aminoferrocene-1-carboxylic acid subunits as turn inducers. / Barišić, Lidija; Čakić, Mojca; Mahmoud, Khaled; Liu, You Nian; Kraatz, Heinz Bernhard; Pritzkow, Hans; Kirin, Srećko I.; Metzler-Nolte, Nils; Rapić, Vladimir.

In: Chemistry - A European Journal, Vol. 12, No. 19, 23.06.2006, p. 4965-4980.

Research output: Contribution to journalArticle

Barišić, L, Čakić, M, Mahmoud, K, Liu, YN, Kraatz, HB, Pritzkow, H, Kirin, SI, Metzler-Nolte, N & Rapić, V 2006, 'Helically chiral ferrocene peptides containing 1′ -aminoferrocene-1-carboxylic acid subunits as turn inducers', Chemistry - A European Journal, vol. 12, no. 19, pp. 4965-4980. https://doi.org/10.1002/chem.200600156
Barišić, Lidija ; Čakić, Mojca ; Mahmoud, Khaled ; Liu, You Nian ; Kraatz, Heinz Bernhard ; Pritzkow, Hans ; Kirin, Srećko I. ; Metzler-Nolte, Nils ; Rapić, Vladimir. / Helically chiral ferrocene peptides containing 1′ -aminoferrocene-1-carboxylic acid subunits as turn inducers. In: Chemistry - A European Journal. 2006 ; Vol. 12, No. 19. pp. 4965-4980.
@article{a372777ed4e04bbdbc9fdd330c74fb20,
title = "Helically chiral ferrocene peptides containing 1′ -aminoferrocene-1-carboxylic acid subunits as turn inducers",
abstract = "We present a detailed structural study of peptide derivatives of 1′-aminoferrocene-1-carboxylic acid (ferrocene amino acid, Fca), one of the simplest organometallic amino acids. Fca was incorporated into di- to pentapeptides with D- and L-alanine residues attached to either the carboxy or amino group, or to both. Crystallographic and spectroscopic studies (circular dicroism (CD), IR, and NMR) of about two dozen compounds were used to gain a detailed insight into their structures in the solid state as well as in solution. Four derivatives were characterized by single-crystal X-ray analysis, namely Boc-Fca-Ala-OMe (16), Boc-Fca-D-Ala-OMe (17), Boc-Fca-β-Ala-OMe (18), and Boc-Ala-Fca-Ala-Ala-OMe (21) (Boc = tert-butyloxycarbamyl). CD spectroscopy is an extremely useful tool to elucidate the hel ical chirality of the metallocene core. Unlike in all other known ferrocene peptides, the helical chirality of the ferrocene is governed solely by the chirality of the amino acid attached to the N terminus of Fca. Depending on the degree of substitution of both cyclopentadiene (Cp) rings, different hydrogen-bonding patterns are realized. 1H NMR and IR spectroscopy, together with the results from X-ray crystallography, give detailed information regarding not only the hydrogen-bonding patterns of the compounds, but also the equilibria between different conformers in solution. Differences in chemical shifts of NH protons in dimethyl sulf oxide ([D6]DMSO) and CDCl3, that is, the variation ratio (vr), is used for the first time as a measure of the hydrogen-bonding strength of individual CO⋯HN bonds in ferrocenoyl peptides. In dipeptides with one intramolecular hydrogen bond between the pendant chains, for example, in dipeptide 16, an equilibrium between hydrogenbonded and open forms is observed, as testified by a vr value of around 0.5. Higher peptides, such as tetrapeptide 21, are able to' form two intramolecular hydrogen bonds stabilizing one single conformation in CDCl 3 solution (vr ≈0). Due to the low barrier of Cp-ring rotation, new and unnatural hydrogen-bonding patterns are emerging. The systematic work described herein lays a solid foundation for the rational design of metallocene peptides with unusual structures and properties.",
keywords = "Amino acids, Bioorganometallic chemistry, Ferrocene, Hydrogen bonds, Peptides",
author = "Lidija Barišić and Mojca Čakić and Khaled Mahmoud and Liu, {You Nian} and Kraatz, {Heinz Bernhard} and Hans Pritzkow and Kirin, {Srećko I.} and Nils Metzler-Nolte and Vladimir Rapić",
year = "2006",
month = "6",
day = "23",
doi = "10.1002/chem.200600156",
language = "English",
volume = "12",
pages = "4965--4980",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "19",

}

TY - JOUR

T1 - Helically chiral ferrocene peptides containing 1′ -aminoferrocene-1-carboxylic acid subunits as turn inducers

AU - Barišić, Lidija

AU - Čakić, Mojca

AU - Mahmoud, Khaled

AU - Liu, You Nian

AU - Kraatz, Heinz Bernhard

AU - Pritzkow, Hans

AU - Kirin, Srećko I.

AU - Metzler-Nolte, Nils

AU - Rapić, Vladimir

PY - 2006/6/23

Y1 - 2006/6/23

N2 - We present a detailed structural study of peptide derivatives of 1′-aminoferrocene-1-carboxylic acid (ferrocene amino acid, Fca), one of the simplest organometallic amino acids. Fca was incorporated into di- to pentapeptides with D- and L-alanine residues attached to either the carboxy or amino group, or to both. Crystallographic and spectroscopic studies (circular dicroism (CD), IR, and NMR) of about two dozen compounds were used to gain a detailed insight into their structures in the solid state as well as in solution. Four derivatives were characterized by single-crystal X-ray analysis, namely Boc-Fca-Ala-OMe (16), Boc-Fca-D-Ala-OMe (17), Boc-Fca-β-Ala-OMe (18), and Boc-Ala-Fca-Ala-Ala-OMe (21) (Boc = tert-butyloxycarbamyl). CD spectroscopy is an extremely useful tool to elucidate the hel ical chirality of the metallocene core. Unlike in all other known ferrocene peptides, the helical chirality of the ferrocene is governed solely by the chirality of the amino acid attached to the N terminus of Fca. Depending on the degree of substitution of both cyclopentadiene (Cp) rings, different hydrogen-bonding patterns are realized. 1H NMR and IR spectroscopy, together with the results from X-ray crystallography, give detailed information regarding not only the hydrogen-bonding patterns of the compounds, but also the equilibria between different conformers in solution. Differences in chemical shifts of NH protons in dimethyl sulf oxide ([D6]DMSO) and CDCl3, that is, the variation ratio (vr), is used for the first time as a measure of the hydrogen-bonding strength of individual CO⋯HN bonds in ferrocenoyl peptides. In dipeptides with one intramolecular hydrogen bond between the pendant chains, for example, in dipeptide 16, an equilibrium between hydrogenbonded and open forms is observed, as testified by a vr value of around 0.5. Higher peptides, such as tetrapeptide 21, are able to' form two intramolecular hydrogen bonds stabilizing one single conformation in CDCl 3 solution (vr ≈0). Due to the low barrier of Cp-ring rotation, new and unnatural hydrogen-bonding patterns are emerging. The systematic work described herein lays a solid foundation for the rational design of metallocene peptides with unusual structures and properties.

AB - We present a detailed structural study of peptide derivatives of 1′-aminoferrocene-1-carboxylic acid (ferrocene amino acid, Fca), one of the simplest organometallic amino acids. Fca was incorporated into di- to pentapeptides with D- and L-alanine residues attached to either the carboxy or amino group, or to both. Crystallographic and spectroscopic studies (circular dicroism (CD), IR, and NMR) of about two dozen compounds were used to gain a detailed insight into their structures in the solid state as well as in solution. Four derivatives were characterized by single-crystal X-ray analysis, namely Boc-Fca-Ala-OMe (16), Boc-Fca-D-Ala-OMe (17), Boc-Fca-β-Ala-OMe (18), and Boc-Ala-Fca-Ala-Ala-OMe (21) (Boc = tert-butyloxycarbamyl). CD spectroscopy is an extremely useful tool to elucidate the hel ical chirality of the metallocene core. Unlike in all other known ferrocene peptides, the helical chirality of the ferrocene is governed solely by the chirality of the amino acid attached to the N terminus of Fca. Depending on the degree of substitution of both cyclopentadiene (Cp) rings, different hydrogen-bonding patterns are realized. 1H NMR and IR spectroscopy, together with the results from X-ray crystallography, give detailed information regarding not only the hydrogen-bonding patterns of the compounds, but also the equilibria between different conformers in solution. Differences in chemical shifts of NH protons in dimethyl sulf oxide ([D6]DMSO) and CDCl3, that is, the variation ratio (vr), is used for the first time as a measure of the hydrogen-bonding strength of individual CO⋯HN bonds in ferrocenoyl peptides. In dipeptides with one intramolecular hydrogen bond between the pendant chains, for example, in dipeptide 16, an equilibrium between hydrogenbonded and open forms is observed, as testified by a vr value of around 0.5. Higher peptides, such as tetrapeptide 21, are able to' form two intramolecular hydrogen bonds stabilizing one single conformation in CDCl 3 solution (vr ≈0). Due to the low barrier of Cp-ring rotation, new and unnatural hydrogen-bonding patterns are emerging. The systematic work described herein lays a solid foundation for the rational design of metallocene peptides with unusual structures and properties.

KW - Amino acids

KW - Bioorganometallic chemistry

KW - Ferrocene

KW - Hydrogen bonds

KW - Peptides

UR - http://www.scopus.com/inward/record.url?scp=33745700281&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33745700281&partnerID=8YFLogxK

U2 - 10.1002/chem.200600156

DO - 10.1002/chem.200600156

M3 - Article

C2 - 16721886

AN - SCOPUS:33745700281

VL - 12

SP - 4965

EP - 4980

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 19

ER -