Wechselwirkungen und Reaktionen von Organometallverbindungen mit Enzymen und Proteinen

Ryabov, Alexander D.

doi:10.1002/ange.19911030806

Cited by 40 publications

(11 citation statements)

References 103 publications

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“…Mass spectrometry confirmed the proposed cation. 1 system for CH 2 (AB part, 2.86 and 3.09 ppm) and CH protons (X part, 5.26 ppm) of the bip ligand owing to chirality of the octahedral ruthenium complex. Imidazole CH protons gave two doublets at 7.19 and 7.22, which integrated for two protons only.…”

Section: Synthesis and Characterization Of Metal Complexesmentioning

confidence: 99%

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The use of 3,3-bis(2-imidazolyl) propionic acid (bip-OH) as a new chelating ligand for Re(CO)3 and Ru complexes: Formation of organometallic PNA oligomers with (bip)Re(CO)3 and their interaction with complementary DNA

Hamzavi¹,

Happ²,

Weitershaus³

et al. 2004

Journal of Organometallic Chemistry

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Section: Synthesis and Characterization Of Metal Complexesmentioning

confidence: 99%

“…Bioorganometallic chemistry is a nascent field of research combining organometallic compounds and reactivity with aspects from biological, pharmaceutical and medicinal chemistry [1][2][3][4]. One prominent use has been the development of new immunoassays which do not rely on radioactive or fluorescent detection.…”

Section: Introductionmentioning

confidence: 99%

The use of 3,3-bis(2-imidazolyl) propionic acid (bip-OH) as a new chelating ligand for Re(CO)3 and Ru complexes: Formation of organometallic PNA oligomers with (bip)Re(CO)3 and their interaction with complementary DNA

Hamzavi¹,

Happ²,

Weitershaus³

et al. 2004

Journal of Organometallic Chemistry

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“…Cyclopentadienyl-Liganden durch das starke 1 H-NMR-Signal oder Ferrocene durch die reversible Oxidation zu Ferrocenium-Ionen. So lassen sich die drei Antiepileptika Carbamazepin, Phenobarbital und Diphenylhydantoin, die mit Co 2 (CO) 6 , Mn(CO) 3 bzw Cr(CO) 3 markiert wurden, gleichzeitig detektieren (Abbildung 10) [30]. Zudem haben Biomoleküle in diesem Bereich ein "spektroskopisches Fenster", d.h. sie absorbieren kaum.…”

Section: Metallorganische Verbindungen Als Marker Für Biomoleküleunclassified

Biometallorganische Chemie: Ein faszinierendes Forschungsgebiet

Beck¹,

Severin²

2002

Chemie in unserer Zeit

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Lange Zeit galten Vitamin B 12 , das Coenzym B 12 sowie Methylcobalamin (Abbildung 3) als einzige natürlich vorkommende Verbindungen mit einer Metall-Kohlenstoff-σ-Bindung [1,10]. Das Coenzym B 12 entsteht durch Reduktion des Cobalt(III)-Corrin-Komplexes über Co II zu dem sehr elektronenreichen Co I -Komplex, an den unter Bildung der Cobalt-Kohlenstoff-σ-Bindung der Adenosylrest von ATP oxidativ addiert wird. Die Rolle des Coenzyms B 12 ist heute sehr gut erforscht. Es katalysiert die ungewöhnliche 1,2-Umlagerung (Abbildung 4), bei der ein Substituent R (z.B. eine Aminogruppe NH 2 ) durch ein H-Atom des benachbarten C-Atoms ausgetauscht wird. Viele Untersuchungen führten zu dem Schluss, dass diese Reaktion über Radikale verläuft. Durch homolytische Spaltung der Co-C-Bindung entsteht ein Adenosyl-Radikal, das ein Wasserstoffatom am C 1 -Kohlenstoff abstrahieren kann. Nach 1,2-Wanderung des Restes R an das benachbarte C-Atom erhält das nun gebildete C 2 Radikal wieder ein H-Atom vom Methyladenosyl, wobei das CH 2 -Adenosyl Radikal regeneriert wird. Das Cobalt-Radikal hat hier quasi "stand by"-Funktion. Eine wichtige weitere metallorganische Verbindung in der Natur ist Methylcobalamin, das aus Cobaltcorrin und einer Methylquelle (Methyltetrahydrofolsäure) entsteht. Methylcobalamin vermag das Methylcarbanion CH 3 − zu übertragen -z.B. entsteht aus Homocystein Methionin -und ist auch verantwortlich für die Biomethylierung von Metallionen, vor allem von Quecksilber(II) (Abbildung 5). Dabei bildet sich das stabile, wasserlösliche Methylquecksilberkation [H 3 C-Hg] + , das die Blut-Gehirn-Schranke überwinden kann und zu schweren Nervenschädigungen führt. Durch Biomethylierung von Sn (aus zinnhaltigen Antifouling-Anstrichen der Schiffe gegen Algen) oder von Arsen (aus dem früher als Malerfarbe verwendeten Schweinfurter Grün = Cuarsenit) entstehen das giftige Me 3 Sn + -Kation bzw. As(CH 3 ) 3 . Es ist sehr bemerkenswert, dass Bakterien im Laufe der Evolution einen Entgiftungsmechanismus für Alkylquecksilber-Kationen entwickelt haben [1,11]. Die Organoquecksilberlyasen (Cystein-haltige Peptide) vermögen die Alkylquecksilber-Kohlenstoff-Bindung zu spalten.Heute weiß man, dass die Cobalt-Kohlenstoff-Bindung eine ganz "normale" Bindung ist (z.B. wie eine Metall-Chlor-Bindung), mit einer Bindungsenthalpie von etwa 100 kJ/mol

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“…Early attempts to reduce benzoylferrocene by the Clemmensen procedure in (9-1-methoxy-2-methylbutane as chiral solvent led to complex mixtures of products with low enantiomeric excess [65]. 4-9b) [68 -701. Microorganisms like baker's yeast are able to reduce some ferrocenyl ketones enantioselectively (for a review on microorganisms and enzymes for the reduction of organometallic compounds, see Ryabov [71]), in particular ketones with electronwithdrawing substituents [72], such as trifluoroacetylferrocene ( Fig. 4-9a) [66].…”

Section: By Asymmetric Synthesismentioning

confidence: 99%

Chiral Ferrocene Derivatives. An Introduction

Wagner¹,

Herrmann²

1994

Ferrocenes

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Soon after its discovery, it was found, that ferrocene behaves in many respects like an aromatic electron-rich organic compound, which is activated towards electrophilic reactions almost like phenol. As a consequence, a rich organic chemistry of ferrocene was developed, in which the organometallic moiety is treated like a simple phenyl group. Thus, Friedel -Crafts acylation leads to ferrocenyl ketones, which can be reduced to secondary ferrocenyl alcohols containing an asymmetric carbon atom. Compounds of this type can be resolved into the enantiomers by standard resolution techniques [l] and do not provide any problems with respect to chemistry and nomenclature. However, ferrocene is different from phenyl with respect to stereochemistry : a derivative with at least two different substituents in the same ring cannot be superimposed with its mirror image, i.e., it is chiral. The first compound of this type to be prepared was 3,1'-dimethyl-ferrocenecarboxylic acid, in which both enantiomers were obtained by resolution of the racemate with cinchonidine and quinidine ( Fig. 4-1) [2]. Crystals of one enantiomer suitable for X-ray structure analysis could be grown; this result confirmed unequivocally the correlation with the true configuration of the molecule [3].Schlogl has investigated the problem systematically and suggested this isomerism to be an example of planar chirality fl, 41. A simple rule was developed to assign chirality descriptors to homoannular di-or polysubstituted ferrocenes: The observer regards the molecule from the side of the ring to be assigned (called the "upper" ring). The substituents are then analyzed for priority according to the Cahn -Ingold -Prelog (CIP) rules. If the shortest path from the substituent with highest priority to that following in hierarchy is clockwise, the chirality descriptor is (R), otherwise it is (S) [5]. If both rings bear at least two different substituents, the process is started with the ring containing the substituent of highest priority, the molecule is then turned upside down and the second ring subsequently assigned. In order to show clearly that the chirality descriptor belongs to a planar element of chirality, it is often written as (,R) or ($), respectively. Another convention exists, which states that in ferrocene derivatives with both central and planar chirality, the descriptor of the central chirality is written first. Thus, (R, S) should mean that the compound contains an element of central chirality with ( R ) configuration and an element of planar chirality with (S) configuration. This order is used in this book. However, the opposite order of the descriptors was suggested in a recent monograph 174

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Wechselwirkungen und Reaktionen von Organometallverbindungen mit Enzymen und Proteinen

Cited by 40 publications

References 103 publications

The use of 3,3-bis(2-imidazolyl) propionic acid (bip-OH) as a new chelating ligand for Re(CO)3 and Ru complexes: Formation of organometallic PNA oligomers with (bip)Re(CO)3 and their interaction with complementary DNA

The use of 3,3-bis(2-imidazolyl) propionic acid (bip-OH) as a new chelating ligand for Re(CO)3 and Ru complexes: Formation of organometallic PNA oligomers with (bip)Re(CO)3 and their interaction with complementary DNA

Biometallorganische Chemie: Ein faszinierendes Forschungsgebiet

Chiral Ferrocene Derivatives. An Introduction

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