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Martin Nieger

Publications and source records attributed to Martin Nieger.

At least 19 recordsLinked to original sources
PubMed2006

Syntheses, pi-stacking interactions and base-pairings of uracil pyridinium salts and uracilyl betaines with nucleobases.

Reaction of 6-chlorouracil with 4-(dimethylamino)pyridine, 4-methylpyridine, and pyridin-4-yl-morpholine yielded pyridinium-substituted uracils as chlorides which were converted into pyridinium uracilates by deprotonation. These heterocyclic mesomeric betaines are cross-conjugated and thus possess separate cationic (pyridinium) and anionic (uracilate) moieties. Calculations and X-ray single crystal analyses were performed in order to characterize these systems and to compare the salts with the betaines. (1)H NMR experiments in D(2)O proved pi-interactions between the uracilyl betaines and adenine, adenosine, as well as adeninium. No pi-stacking interactions were detected between the betaines and guanosine. The acidic N8-H group of the uracil pyridinium salts caused acid-base reactions which were observed in parallel to pi-stacking interactions. Self-complementarity of the modified uracils was detected by (1)H NMR experiments in DMSO-d(6) and electrospray ionisation mass spectrometry (ESIMS). Ab initio calculations predicted base-pairings of the modified uracils with adeninium, cytosine, and guanine. Several geometries of hydrogen-bonded associates were calculated. Hoogsteen pairings between the uracil-4-(dimethylamino)pyridinium salt and adeninium, as well as associates between the corresponding betaine plus cytosine, and the betaine plus guanine were calculated, and the most stable conformations were determined. In the ESI mass spectra, prominent peaks of associates between the modified uracils and adeninium, cytosine, cytidine, guanosine and d(CpGp) were detected.

Base Pairing↗
PubMed2006

The homologous series of 1,1'-ferrocenylenebisdihalophosphanes (C5H4PX2)2Fe (X = F, Cl, Br, I): precursors for the first metallocene bridged bisphosphaalkene.

A facile synthetic access to the homologous series of 1,1'-ferrocenylene bisdihalophosphanes Fc'(PX2)2 (X = F, Cl, Br, I; Fc' = 1,1'-ferrocenediyl = ferrocenylene = -C5H4FeC5H4-) is reported. The 31P NMR spectroscopic data of this series suggest a similar electronic interaction of the -PX(2) unit with the ferrocene system as in monofunctional ferrocenyldihalophosphanes. Crystal structures for Fc'(PCl2)2 and Fc'(PBr2)2 reveal that the nature of the halogen atom within the phosphane unit strongly influences the twist angle of the ferrocene system, while leaving the other structural parameters mostly unaffected. Based on these bisdihalophosphanes, a synthetic access to the first metallocene bridged bisphosphaalkene ((C5H4P=C(t-Bu)OTMS)2Fe) is reported in which the tert-butyl substituents provide sufficient steric pressure to control the E/Z isomeric ratio which leads to the almost exclusive formation of the most stable Z,Z isomer out of the three possible isomers.

Journal Article↗
PubMed2006

Synthesis of small tripeptide molecules through a catalysis sequence comprising metathesis and aminohydroxylation.

Tripeptidic structures were synthesized by using a combination of two independent consecutive catalytic procedures. Cross-metathesis of N-acroyl amino acid esters yields fumaric amide compounds with exclusive E double-bond geometry. This represents an unprecedented example of complete double-bond selectivity in this kind of reaction. A subsequent asymmetric aminohydroxylation of the chiral fumaric amides was carried out without the need of any further ligand and gave high yields and no side products. This reaction transforms the central fumaric amide unit into a hydroxy aspartic acid moiety and relies on the inherent stereochemistry of the starting fumaric diamides. An additional feature of our sequence is the ease of generating stereochemical diversification within the aminohydroxylation reaction. As a consequence, rapid conformational and configurational diversification can be achieved from the overall two-step catalytic sequence. The versatility of this approach is demonstrated by starting from two different N-acroyl amino esters, which led to the synthesis of eight structurally and stereochemically different tripeptides that could all be identified individually. As such, the present two-step catalytic approach should serve to efficiently synthesize large families of tripeptidic molecular probes.

Amides↗
PubMed2006

Diastereoselective synthesis of highly functionalized tetrahydroxanthenols--unprecedented access to privileged structural motifs.

Tetrahydroxanthenones, which can be easily prepared by a domino oxa-Michael aldol condensation, offer various possibilities for diastereoselective functionalization, giving access to the stereocontrolled synthesis of stereochemical triades or tetrades, which represent privileged structural motifs. In most cases, the relative stereochemistry was unequivocally established by crystal structure analysis.

Aldehydes↗
PubMed2006

A supramolecular fluorescence probe for caffeine.

[structure: see text] Supramolecular sensing is rather limited to charged analytes. This report describes a practicable assay for caffeine, which employs a competitive "indicator-displacement" approach and allows detection by fluorescence. A simple analytical protocol is described that allows quantitation of caffeine in beverages.

Biosensing Techniques↗
PubMed2006

P-hydrogen-substituted 1,3,2-diazaphospholenes: molecular hydrides.

P-Hydrogen-substituted 1,3,2-diazaphospholenes 1 were prepared by an improved procedure from diazadienes and were characterized by spectroscopy and in one case by X-ray diffraction. A unique hydride-type reactivity of the P-H bonds was documented by extensive reactivity studies. Aldehydes and ketones were readily reduced to diazaphospholene derivatives of the corresponding alcohols, with alkyl-substituted ketones being converted at much lower rates than aldehydes or diaryl ketones. Reactions with the tetrachlorides of group 14 elements proceeded via hydride/chloride metathesis to give either partially chlorinated derivatives EH(n)Cl(4-n) (n = 0-3 for E = C, Si) or HCl and phosphenium salts 16c[ECl3] (for E = Ge, Sn) which were characterized by spectroscopic and X-ray diffraction studies. Tin dichloride was readily reduced to the element. Reactions of 1c with the P-chloro-diazaphospholene 3c and the salt 16c[OTf] allowed the first experimental detection of intermolecular exchange of a hydride, rather than a proton, between phosphine derivatives. Computational studies indicated that the hydride transfer between 1c and the cation 16c involves a transient H-bridged species with bonding properties similar to those of B2H7-. The preference for the formation of these bridged intermediates over P-P bonded phosphenium-phosphine adducts is attributed to the low electrophilicity of the diazaphospholenium cations and characterizes a novel reaction mode for phosphenium ions.

Journal Article↗
PubMed2006

The transfer of tin and germanium atoms from N-heterocyclic stannylenes and germylenes to diazadienes.

New N-heterocyclic stannylenes and germylenes were synthesized by transamination of E[N(SiMe3)2] (E = Ge, Sn) with alpha-amino-aldimines or ethylidene-1,2-diamines and were characterized by spectroscopic methods and in the case of the germylene 10 g by X-ray diffraction. The reactions of several germylenes and stannylenes with diazadienes were studied by using dynamic NMR and computational methods. Experimental and theoretical studies confirmed that metathesis with exchange of the Group 14 atom is feasible for both stannylenes and germylenes, with exchange rates being generally higher for stannylenes. The metathesis of the diazadiene 3 b and the stannylene 1 b follows second-order kinetics and exhibits a sizeable negative entropy of activation. The transfer reaction is inhibited by bulky substituents in both reactants and surprisingly coincides with a suppression of the fragmentation of the stannylene into tin and diazadiene. A connection between oxidative addition and ring fragmentation was also observed in the reaction of 1 f with sulfur. Density functional theory (DFT) calculations suggest that all metathesis reactions proceed via transient spirocyclic [1+4] cycloaddition products, the formation of which is generally endothermic and endergonic. The spirostannanes display a distorted Psi-tbp geometry at the tin atom and their cycloreversion requires low or nearly negligible activation energies; spirogermanes exhibit distorted tetrahedral central atoms and sizeable energy barriers with respect to the same reaction. Complementary studies of cycloadditions of diazadienes to triplet germylenes or stannylenes indicate that these reactions are exothermic. The lowest triplet state in the carbene homologues results from promotion of an electron from an n(N) orbital with pi character rather than the n(C)-sigma orbital as in carbenes, and singlet-triplet excitation energies decrease from carbon to tin. Spirostannanes exhibit a triplet ground-state multiplicity that implies that the energy hypersurfaces for the reactions of singlet and triplet stannylenes with diazadienes intersect; for germylenes, the singlet hypersurface is always lower in energy. A reaction mechanism explaining the different thermal stabilities of N-heterocyclic germylenes and stannylenes, and the coincidence between ring metathesis and thermal decomposition of the latter, is proposed based on the different separation of the singlet and triplet energy hypersurfaces.

Journal Article↗
PubMed2005

Palladium(II)-catalyzed intramolecular diamination of unfunctionalized alkenes.

Intramolecular diamination reactions are described which yield cyclic ureas as direct products of an oxidative alkene transformation in the presence of palladium acetate and iodosobenzene diacetate as terminal oxidant. The reaction is truly catalytic in metal catalyst and represents the proof of principle for this elusive type of alkene oxidation.

Alkenes↗
PubMed2005

From uncharged to decacationic molecules: syntheses and spectroscopic properties of heteroarenium-substituted pyridines.

Nucleophilic substitutions on pentachloropyridine with 4-(dimethylamino)pyridine, 4-aminopyridine, and 4-(pyrrolidin-1-yl)pyridine give mono-, tri- and pentacationic pyridine-hetarenium salts. The mono-, tri- and pentacationic 4-aminopyridine derivatives can be deprotonated to neutral compounds in solution, or protonated to di-, hexa- and decacationic pyridine derivatives, respectively. Successive substitutions with different heteroaromatic nucleophiles give pyridines with two distinct types of heteroarenium substituents.

Cations↗
PubMed2005

Tuning haptotropic rearrangements of arene-chromium complexes: steric and electronic effects of phosphorus coligands.

(Eta6-arene)tricarbonylchromium 2 was synthesised by [3+2+1] benzannulation of the Fischer carbene complex 1 and converted to the thermodynamically more favorable regioisomer 3 by haptotropic metal migration. Photo-induced ligand-exchange reactions in both regioisomers with triphenylphosphine, triphenylphosphite, trimethylphosphine, and trimethylphosphite afforded dicarbonyl(phosphine or phosphite)arene complexes 4-11. The regioisomers were separated by high-performance liquid chromatography (HPLC), and kinetic analyses of the thermo-induced haptotropic metal shift were performed with regioisomers 4, 6, 8, and 10. The kinetic parameters were compared with those obtained for the parent tricarbonyl complex 2 and were discussed in terms of the steric and electronic properties of the phosphorus ligands by applying a quantitative analysis of ligand effects (QALE). The molecular structures of regioisomeric PPh3 and P(OPh)3 complexes 4/5 and 6/7 as well as of P(OMe)3 complex 10 have been established by single-crystal X-ray analysis.

Journal Article↗
PubMed2005

Surprising reactions of a 2H-azaphosphirene complex with a silylene.

Reaction of the 2H-azaphosphirene complex with the silylene yielded the bicyclic carbene complex as sole product at ambient temperature; the reaction was less selective at elevated temperatures; additionally, the synthesis and structure of the first 1,2,4,3-azadiphosphasilol-5-ene complex is presented.

Alkenes↗
PubMed2005

A modular and efficient synthesis of functional titanocenes.

A modular synthesis of functional titanocenes featuring building blocks is described. The approach allows straightforward access to large numbers of structurally diverse titanocenes that are pertinent for catalysis, structural studies, and bioinorganic chemistry. Among the functional groups introduced are amino acids, sugars, and fluorescence labels that are attached to the cyclopentadienyl ligand as esters and amides.

Crystallography, X-Ray↗
PubMed2005

From model compounds to extended pi-conjugated systems: synthesis and properties of dithieno[3,2-b:2',3'-d]phospholes.

To explore their suitability for applications in molecular optoelectronics and as sensory materials, novel dithieno[3,2-b:2',3'-d]phospholes have been synthesized and their reactivity and properties investigated. An efficient two-step synthesis allowed for a modular assembly of differently functionalized compounds. The dithieno[3,2-b:2',3'-d]phosphole system exhibits extraordinary optoelectronic properties with respect to wavelength, intensity, and tunability. Owing to the nucleophilic nature of the central phosphorus atom, its significant electronic influence on the conjugated pi system can be altered selectively by chemically facile modifications such as oxidation or complexation with Lewis acids or transition metals. All the dithienophosphole species presented show very strong blue photoluminescence with excellent quantum yield efficiencies supporting their potential utility as blue-light emitting components in organic light emitting diodes (OLEDs). Furthermore, depending on the electronic nature of the phosphorus center, the materials exhibit distinctive optoelectronic properties suggesting that the dithieno[3,2-b:2',3'-d]phosphole system may be useful as sensory material. Theoretical calculations, including time-dependent DFT methods, revealed the excellent predictability of the structures and optoelectronic properties of the functionalized dithienophospholes allowing the design of future dithieno[3,2-b:2',3'-d]phosphole-based materials to be "stream-lined". By using tin-functionalized dithienophosphole monomers, a strategy, which involves Stille coupling, towards extended pi-conjugated materials with significantly redshifted optoelectronic properties is also presented.

Journal Article↗
PubMed2005

Structurally diverse second-generation [2.2]paracyclophane ketimines with planar and central chirality: syntheses, structural determination, and evaluation for asymmetric catalysis.

A set of 20 novel [2.2]paracyclophane ketimines with planar and central chirality has been synthesized from enantiomerically pure and racemic 5-acyl-4-hydroxy[2.2]paracyclophane and alpha-branched chiral amines. Their X-ray structures were determined to elucidate the three-dimensional structures and the absolute configuration. The ketimines were used as catalysts in the asymmetric 1,2-addition reactions of diethylzinc with substituted benzaldehydes to furnish chiral alcohols in up to 95 % ee.

Journal Article↗
PubMed2005

First osmium-catalysed ketamination of alkenes.

Conditions for a first oxidative conversion of alkenes into 2-amino ketones are described, which yield racemic products within a direct oxidation pathway and 2-amino ketones with up to 99% enantiomeric excess from the corresponding enantiopure amino alcohols.

Alkenes↗