Asymmetric solution-phase mixture aldol reaction using oligomeric ethylene glycol tagged chiral oxazolidinones

Sorting tags are oligomeric structures that can be used as protecting groups or chiral auxiliaries enabling solution-phase mixture syntheses of multiple tagged compounds in one pot and allowing for facile and predictable chromatographic separation of products at the end of synthetic sequences. Perfluorinated hydrocarbon and oligomeric ethylene glycol (OEG) derivatives are known classes of sorting tags. Herein we describe the preparation of OEGylated chiral oxazolidinones and their use in asymmetric solution-phase mixture aldol reactions. Through the use of such oxazolidinones based on tyrosine four different individually tagged aldol adducts were obtained as a mixture, chromatographically demixed, detagged, and it was shown that these processes gave the desired aldol products in good yield and enantioselectivity.     

Synthesis, photophysical and electrophosphorescent properties of fluorene-based platinum(II) complexes

A series of platinum(II) complexes bearing tridentate cyclometalated C^N^N (C^N^N=6-phenyl-2,2'-bipyridine and π-extended R-C^N^N=3-[6'-(naphthalen-2'-yl)pyridin-2'-yl]isoquinoline) ligands with fluorene units have been synthesised and their photophysical properties have been studied. The fluorene units are incorporated into the cyclometalated ligands by a Suzuki coupling reaction. An increase in the π-conjugation of the cyclometalated ligands confers favourable photophysical properties compared to the 6-phenyl-2,2'-bipyridine analogues. The fluorene-based platinum(II) complexes display vibronic-structured emission bands with λ(max)=558-601 nm, and high emission quantum yields up to 0.76 in degassed dichloromethane. Their emissions are tentatively assigned to excited states with mixed (3)IL/(3)MLCT parentage (IL=intraligand, MLCT=metal-to-ligand charge transfer). The crystal structures of these platinum(II) complexes reveal extensive Pt(II)···π and/or π-π interactions. The fluorene-based platinum(II) complexes are soluble in organic solvents, have high thermal stability with decomposition temperature >350 °C, and can be thermally vacuum-sublimed or solution-processed as phosphorescent dopants for the fabrication of organic light-emitting diodes (OLEDs). A monochromic OLED with 3d as dopant (2 wt%) fabricated by vacuum deposition gave a current efficiency of 14.7 cd A(-1) and maximum brightness of 27000 cd m(-2). A high current efficiency (9.2 cd A(-1)) has been achieved in a solution-processed OLED using complex 3f (5 wt%) doped in a PVK (poly(9-vinylcarbazole)) host.     

Recent Progress towards Transition‐Metal‐Catalyzed Synthesis of Fluorenes

Fluorenes are a commonly encountered structural motif in materials science, pharmaceutical chemistry, and organic synthesis. Among various strategies towards the synthesis of this unique structure, transition metal‐catalyzed functionalization has emerged as one of the most efficient methods. This Minireview presents an overview of the recent advances in this emerging area by highlighting the reactions’ specificity and applicability and, where possible, provides a mechanistic rationale.     

Interaction of giant extracellular Glossoscolex paulistus hemoglobin (HbGp) with zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS): effects of oligomeric dissociation

The present work focuses on the interaction between the zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp). Electronic optical absorption, fluorescence emission and circular dichroism spectroscopy techniques, together with Gel-filtration chromatography, were used in order to evaluate the oligomeric dissociation as well as the autoxidation of HbGp as a function of the interaction with HPS. A peculiar behavior was observed for the HPS–HbGp interaction: a complex ferric species formation equilibrium was promoted, as a consequence of the autoxidation and oligomeric dissociation processes. At pH 7.0, HPS is more effective up to 1 mM while at pH 9.0 the surfactant effect is more intense above 1 mM. Furthermore, the interaction of HPS with HbGp was clearly less intense than the interaction of this hemoglobin with cationic (CTAC) and anionic (SDS) surfactants. Probably, this lower interaction with HPS is due to two factors: (i) the lower electrostatic attraction between the HPS surfactant and the protein surface ionic sites when compared to the electrostatic interaction between HbGp and cationic and anionic surfactants, and (ii) the low cmc of HPS, which probably reduces the interaction of the surfactant in the monomeric form with the protein. The present work emphasizes the importance of the electrostatic contribution in the interaction between ionic surfactants and HbGp. Furthermore, in the whole HPS concentration range used in this study, no folding and autoxidation decrease induced by this surfactant were observed. This is quite different from the literature data on the interaction between surfactants and tetrameric hemoglobins, that supports the occurrence of this behavior for the intracellular hemoglobins at low surfactant concentration range. Spectroscopic data are discussed and compared with the literature in order to improve the understanding of hemoglobin–surfactant interaction as well as the acid isoelectric point (pI) influence of the giant extracellular hemoglobins on their structure–activity relationship.     

Two novel carbonic acid esters conjugated with oligophenyl glucosides from Rhamnus nakaharai

Two novel carbonic acid esters conjugated with oligomeric phenyl glycosides have been isolated and characterized from the wood of Rhamnus nakaharai. The structures are characterized as 5,7-dihydroxyphthalide 5-O-β-[6-O-{3″-methoxy-4″-O-β-[6?-O-(4?-O-carboxy-3?,5?-dimethoxy)phenyl]glucopyranosyl}phenyl]glucopyranoside (1) and 6-O-{3′-methoxy-4′-O-β-[6″-O-(3?-mercapto-5?-methoxy-4?-O-methylcarboxy)phenyl]glucopyranosyl}phenyl β-glucopyranose (2), namely, rhamnakoside A (1) and B (2), all by NMR and other spectral methods, respectively. They could be a novel case of phase II detoxification products and biogenetic diversity in plant kingdom.     

Synthesis of Nonionic Oligomeric Manganese（ Ⅱ ） Complexes and Investigation of Their Toxicity and T1 -Relaxation Enhancement

Six nonionic oligomeric manganese （ Ⅱ ） complexes with oligomeric phosphate-polyglycol-EDTA ester ligands were synthesized and characterized. The longitudinal relaxivities of these complexes were measured. One of these complexes, which showed the highest relaxivity, was chosen to be used in the acute toxicity test and the T1-weighted imaging experiment. It has been found that compared to Gd-DTPA, this nonionic oligomeric Mn（ Ⅱ ） complex exhibits no acute toxicity, generates highly enhanced MRI signals and increases the intention time in the rat liver tissue.     

Synthesis,Design and Electrochemical Properties of Langmuir–Blodgett (LB) Films Built of Bis(Pyrrolyl)Fluorene

The synthesis, characterization, electropolymerization, electrical and sensing properties of LB films of mono‐ and dihexadecyl‐bis(pyrrolyl)fluorene derivatives are reported. Different responses to different gases at various concentrations obtained for mono‐ and disubstituted derivatives of bis(pyrrolyl)fluorene make these materials a very good candidates for elements of gas sensing devices of the different type of an “artificial nose” or a neuronic network.     

Influence of temperature and mobile phase composition on retention properties of oligomeric bonded phases in reversed-phase liquid chromatography (RPLC)

Summary The effect of temperature and mobile phase composition (methanol-water) on the retention behaviour of an oligomeric series of n-octylsilyl bonded phases in reversed-phase liquid chromatography has been investigated. Plots of lnk against 1/T (van't Hoff plot) and the enthalpy of transfer (ΔH^o) yields linear relationships under the conditions studied. The ΔH^o values of the aromatic hydrocarbons and n-alkyl benzoates are higher than those of the polar compounds due to their higher level of interaction with the stationary phase. A linear plot of ΔH^o vs. ΔS^o suggest that the retention process, which is essentially controlled by non-specific (dispersive) interactions between the solutes and the bonded ligands, is identical for all cases evaluated. The existence of similar retention mechanisms is confirmed by the constant value of the enthalpy-entropy compensation temperature of the columns for a given class of componds. As expected, decreasing the methanol content (% v/v) of the mobile phase results in increased eluite retention times. The methylene and phenyl selectivities are found to be independent of the carbon content of the stationary phases and varied only with the eluent composition. In addition to their high stability under aggressive mobile phase conditions as previously reported, the results of this study generally showed that the solute retention process on oligomeric phases are similar to those exhibited by the conventional reversed phases.     

Functionalization of azafullerene C59N. Radical reactions with 9-substituted fluorenes

An efficient reaction between the azafullerene dimer, (C₅₉N)₂ and 9-substituted fluorenes leads to the formation of four new azafullerene monoadducts.     

Characterization of mixtures of biocidal oligoguanidines by capillary electrophoresis and high-performance liquid chromatography coupled to mass spectrometry

The polycondensation of guanidine hydrochloride and 2,2′-(ethylenedioxy)bis(ethylamine) leads to various types of oligomeric guanidines exhibiting a broad spectrum of biocidal activities. In the present work a reversed-phase high-performance liquid chromatographic method with a gradient consisting of aqueous 0.1% trifluoroacetic acid and acetonitrile as mobile phase has been developed to separate these oligoguanidines according to type and chain length. The combination with electrospray mass spectrometry allowed the identification of the various compounds. By this technique, some structures already suggested in the literature could be confirmed, and several additional oligoguanidines not yet reported could be identified. As a complementary technique, capillary zone electrophoresis was investigated. Best results were obtained with carrier electrolytes consisting of phosphoric acid in water/acetonitrile mixtures. Although the number of peaks that could be separated by the electrophoretic method was considerably lower than in case of the chromatographic method, capillary electrophoresis in combination with UV detection at 195 nm may still be a fast method suitable for quantitation of some of the major compounds and for monitoring the reaction rate during the polycondensation reaction.