Nucleophilic ring opening reactions of aziridines

Aziridine ring opening reactions have gained tremendous importance in the synthesis of nitrogen containing biologically active molecules. During recent years, a great effort has been put forward by scientists toward unique bond construction methodologies via ring opening of aziridines. In this regard, a wide range of chiral metal- and organo-catalyzed desymmetrization reactions of aziridines have been reported with carbon, sulfur, oxygen, nitrogen, halogen, and other nucleophiles. In this review, an outline of methodologies adopted by a number of scientists during 2013–2017 for aziridine ring opening reactions as well as their synthetic applications is described.     

Preparation of 1,3-disubstituted isoquinoline derivatives from N-boc-3-substituted-1,2-dihydroisoquinolines

3-Substituted N-Boc-1,2-dihydroisoquinolines 2 can be functionalized at the 1-position via lithiation and subsequent electrophilic trapping. The resulting products 3 can be deprotected and oxidized to afford the corresponding 1,3-disubstituted isoquinolines 5 . Deprotection of dihydroisoquinoline 3k followed by sodium borohydride reduction affords the cis-1,3-disubstituted tetrahydroisoquinoline 11 . The 1,3-disubstituted N-Boc-1,2-dihydroisoquinoline 3g is efficiently alkylated at the 1-position to give 1,1,3-trisubstituted analogs 12 .     

Partial oxidation of methane over biomass fly ash (BFA)-supported Ni/CaO catalyst for hydrogen-rich syngas production

Research on Chemical Intermediates - In this study, biomass fly ash (BFA)-supported Ni/CaO catalyst was synthesized, characterized and evaluated for partial oxidation of methane (POM) in a fixed...     

Synthetic strategies toward the synthesis of enoxacin-, levofloxacin-, and gatifloxacin-based compounds: A review

Enoxacin, levofloxacin, and gatifloxacin represent one of the most important prerogative scaffolds in drug development. They possess broad spectrum antimicrobial and anti-inflammatory activities. They inhibit bacterial growth by blocking their topoisomerase enzyme which is necessary for the proper functioning of bacterial DNA. In this article, we have reviewed the synthetic approaches involved in the synthesis of derivatives of enoxacin, levofloxacin, and gatifloxacin.     

Structural distinction between sabandins A and B from Artemisia scoparia waldst. (Asteraceae)

The three possible isomeric structures of the sabandin coumarin were published by Reyes and Gonzalez in 1970. We have isolated two of these isomers sabandins A and B from Artemisia scoparia (Asteraceae) and distinguished by NOE difference NMR measurements.     

Warm Gauge-Flation with General Dissipative Coefficient

In this work, we study the effects of generalized dissipative coefficient on the slow-roll inflation driven by non-Abelian gauge field minimally coupled to gravity. The dynamics of warm intermediate and logamediate inflationary models during weak and strong dissipative regimes is analyzed. In both cases, we explore effective scalar potential, slow-roll parameters, scalar and tensor power spectra, scalar spectral index and tensor to scalar ratio under slow-roll conditions. We conclude that our gauge-flationary model with generalized dissipative coefficient remains consistent with the recent data for dissipative parameter m = 3 and m = 1 for weak and strong dissipative eras, respectively.     

Voltammetric reduction of 2-(4′-N,N-dimethylaminostyryl)-1-ethyl pyridinium iodide inDMF

The voltammetric reduction mechanism of 2-(4-dimethylaminostyryl)-1-ethyl pyridinium iodide at the hanging dropping mercury electrode has been studied in N,N-dimethylformamide solution containing 0.1 mol dm^–3 tetraethylammonium perchlorate. The depolarizer is reduced via a single diffusion-controlled irreversible two-electron cyclic voltammetric wave. The wave is attributed to the reduction of the azomethine bond of the pyridinium nucleus. Cyclic voltammetric studies indicate that the cv wave follows an ECE mechanism. The chemical reaction is proposed to be a protonation.

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Voltammetrische Reduktion von 2-(4-N,N-Dimethylaminostyryl)-1-ethyl-pyridiniumjodid inDMF

Zusammenfassung Es wurde der voltammetrische Reduktionsmechanismus von 2-(4-N,N-Dimethylaminostyryl)-1-ethyl-pyridiniumjodid in Dimethylformamid-Lösung mit einem Tetraethylammoniumperchlorat-Gehalt von 0.1 mol dm^–3 an der tropfenden Quecksilberelektrode untersucht. Der Depolarisator wird über eine einzige diffusionskontrollierte irreversible Zweielektronenwelle reduziert. Diese Welle wird der Reduktion der Azomethinbindung des Pyridinium-Kerns zugeordnet. Cyclische voltammetrische Untersuchungen zeigen, daß die CV-Welle einem ECE-Mechanismus folgt. Als chemische Reaktion tritt Protonierung ein.

     

Convolution-deconvolution cyclic voltammetric equilibria study on cadmium(II)-L-histidinate in aqueous solutions

POLAG computer programme was employed for processing convoluted-deconvoluted cyclic voltammetric data to study cadmium(II)-L-histidinate system. This was performed in 0.1 mol/dm(3) NAClO(4) aqueous solution at different pH's at 298K. The results show that the reduction of cadmium(II) and its complexes proceeds via a reversible and diffusion-controlled wave of two electrons at the entire range of pH. The system was studied at two ranges of pH (6.73-7.44 and 8.53-8.92). It was evident that the system at the first range of pH is well described by the presence of a mixture of binary complexes, [Cd(HisO.H)], [Cd(HisO.H(2))(2)] and a ternary one [Cd(HisO.H)(HisO.H(2))]. For the second pH range, it was revealed that the most likely model corresponds to the presence of a mixture of [Cd(HisO)(2)] and [Cd(OH)] species. The overall stability constants were computed. The structure of the detected complexes was discussed on the basis of ligating sites of histidine.     

On- and off column enantiomerization of 4,4′-bisquinolin-2-ones: A comparison of Auto-, DHPLcy2k and DCXplorer calculated thermodynamic data generated by dynamic high,performance liquid chromatography with theoretically calculated data

Fast semipreparative HPLC enantioseparation of four axially chiral biscarbostyrils (4,4′-bisquinoline-2-ones) using ULMO as a π-acidic Pirkle type chiral stationary phase leads to two racemizing pairs (1,2; k_obs 1.6 × 10⁻⁴ and 3.0 × 10⁻⁴ s⁻¹ at 28 °C) and two stable ones (3,4). 3 was stabilized by a crown ether linkage from pos. 6 to 6′, and 4 had sterically demanding bromo substituents in pos. 3 and 3′. On-column generated temperature-dependent chromatograms of 1 and 2 were fitted with Auto-DHPLCy2k and DCXplorer. For cpd 2 both programs delivered similar ΔG values of 90 and 93 kJ/mol, well comparable with the 99 kJ/mol calculated with the B3LYP/6-31G (d) procedure. At temperatures of high conversion DCXplorer delivered inconsistent series of rate constants for the more tailing and less resolved tetramethoxy derivative 1. We connect this problem with an almost impossible halfwidth calculation of tailing peak pairs which are weakly resolved. However, this problem could be observed only in the case of tetramethoxy derivative 1. Stochastic generated data of Auto-DHPLCy2k could be used at a lower percentage of conversion only while the theoretical plate model did not deliver useful data at temperatures of very low conversion but fitted well high conversion chromatogram series of 1 and 2.     

The effect of the number of carbohydrate moieties on the azaphthalocyanine properties

A series of azaphthalocyanines (AzaPc) bearing one, two, four or eight isopropylidene-protected galactosyl units was prepared by azide-alkyne click reaction or by classical Pc template cyclotetramerization of the corresponding dicyanopyrazine and AzaPc properties important for photodynamic therapy were compared. All compounds absorbed at long wavelengths (above 650 nm) and belonged to strong singlet oxygen producers (Φ(Δ) = 0.58-0.64) retaining significant fluorescence emission (Φ(F) = 0.026-0.23). The only exception was the compound with four isopropyliden-protected galactosyl units where partial aggregation was observed. Removal of protecting groups increased the polar character of all AzaPc. However, only AzaPc bearing eight galactoses was found to be water-soluble (105 mg mL(-1)) but noticeably aggregated in water as well as in organic solvents (DMF, DMSO). Amphiphilic AzaPc bearing one deprotected galactose was incorporated into the lipidic bilayer of liposomes in a nonaggregated form. Liposomes may therefore be a suitable delivery system for this amphiphilic photosensitizer.