Straightforward methodology for the enantioselective synthesis of benzo[a]- and indolo[2,3-a]quinolizidines

An enantioselective two-step route to substituted benzo[a]- and indolo[2,3-a]quinolizidines has been developed. It consists of (i) a stereoselective cyclocondensation of a racemic or prochiral delta-oxo(di)ester with either (S)-(3,4-dimethoxyphenyl)alaninol or (S)-tryptophanol in a process involving a dynamic kinetic resolution and/or the differentiation of enantiotopic or diastereotopic ester groups, and (ii) a subsequent stereocontrolled cyclization on the aromatic ring taking advantage of the masked N-acyl iminium ion present in the resulting oxazolopiperidone lactams.     

Magneto-structural correlations in binuclear copper(II) compounds bridged by a ferrocenecarboxylato(-1) and an hydroxo- or methoxo-ligands

The syntheses, characterization and X-ray crystal structures of the first two examples of asymmetrically bridged dinuclear copper(ii) complexes containing a ferrocenecarboxylato ligand and a methoxo group in [{Cu(dmen)}2(micro-OMe){micro-O2C(eta5-C5H4)Fe(eta5-C5H5)}](ClO4)2, 1, (dmen=N,N-dimethylethylenediamine) or an hydroxo group in [{Cu(tmen)}2(micro-OH){micro-O2C(eta5-C5H4)Fe(eta5-C5H5)}](ClO4)2, 2 , (tmen=N,N,N'N'-tetramethylethylenediamine) are reported. Magneto-chemical studies revealed that 1 and 2 exhibit opposite superexchange interactions between the two Cu(II) paramagnetic centers: an antiferromagnetic coupling (J = -11 cm(-1)) in 1 and a ferromagnetic interaction (J = +29 cm(-1)) in 2. The results obtained from these studies suggest that the weak interactions between the Cu(II) ions and the perchlorate anions detected in the crystal structures are important to introduce significant distortions in the heterobridged [Cu2(micro-OR){micro-O2C(eta5-C5H4)Fe(eta5-C5H5)}]2+ cores of 1 and 2, which clearly affect the nature and strength of the superexchange interactions. Computational studies based on density functional theory and ab initio multiconfigurational second-order perturbation theory (CASPT2) calculations have also been performed in order to rationalize the magnetic behaviour of 1 and 2. The magneto-structural correlations for complexes containing the [Cu(micro-OR)(micro-O2CR')Cu] core are discussed, and the relevance of the out-of-plane angle of the R group with the Cu(micro-OR)Cu plane established.     

2′,6′-Dimethoxyflavone as an Aid to the Crystallization of Benzoic Acids and X-Ray Structure of the Inclusion Compound with 2,4,6-Trimethoxybenzoic Acid

The crystal structure of the inclusion compound formed between 2-6-dimethoxyflavone and 2,4,6-trimethoxybenzoic acid has been investigated by single-crystal X-ray analysis. The compound crystallizes in the triclinic system, space group P-1, as do inclusion compounds with acetic, propionic, and bromoacetic acids. However, the larger 2,4,6-trimethoxybenzoic acid molecule induces a layered structure.     

Creatinine determination in urine samples by batchwise kinetic procedure and flow injection analysis using the Jaffé reaction: chemometric study

The classical Jaffé reaction for the determination of creatinine in urine samples is tested. A comparative study of the main analytical characteristics focussed to minimize the bias error and improve the precision, for the batchwise and flow injection (FI) methods is realized. Also, the effect of the albumin concentration in the determination of creatinine has been studied. Different analytical signals were studied. Absorbance increments at different times permit to estimate the creatinine concentration free from bias error in urine by the batchwise method using the calibration graph obtained with creatinine standards and no measurement of the blank solution is needed. The lineal interval was 0.92-50 mg l(-1) and seven samples can be processed per hour by an operator. No previous treatment of the urine sample is necessary. The FI method provides also good results. The lineal interval was 30-100 mg l(-1) and the sample rate was around 20 samples per hour. If increased albumin levels are detected in the urine, standard addition method or the calibration graphs with standards in presence of albumin are needed in order to obtain accurate results when FI method is employed. The obtained accuracy of the both methods allows its application as diagnostic tool to establish the urinary creatinine levels.     

Synthesis, characterization and structure of diiron organometallic derivatives of 2,9-dimethyl-1,10-dihydro-dicyclopenta[a,h]naphthalene

A new fused ring compound 2,9-dimethyl-1,10-dihydro-dicyclopenta[a,h]naphthalene (VI), (H₂L), has been synthesized from naphthalic anhydride. Two organometallic binuclear complexes, [Cp*Fe-L-FeCp*] (1) and the mixed valence compound, (2) have been characterized by spectroscopic and electrochemical techniques. The structure resolution of (1) by single crystal X-ray diffraction shows that the two organometallic fragments Cp*Fe are in an anti position. Cyclic voltammetry exhibits a potential difference of 348 mV between both redox peaks. The Mössbauer investigation at different temperatures shows a uniform environment for the neutral compound (1) and two sites, assigned to Fe²⁺ and Fe³⁺ for the compound (2). The information gathered by all the previously mentioned techniques indicates that the studied binuclear complex belongs to the mixed valence class II complexes according to the classification of Robin and Day.     

Polymer-filled nanoporous silica aerogels as hosts for highly stable solid-state dye lasers

New hybrid solid-state dye laser materials based on highly porous silica aerogels have been synthesized. The open porous network of the aerogel was saturated with laser dyes dissolved in appropriate organic monomers, and polymerization took place inside the silica structure. The resulting polymer-filled nanoporous aerogel (PFNPA) was cast in a cylindrical shape, forming monoliths that were used as gain media in solid-state dye lasers. When the PFNPA incorporated pyrromethene dyes, highly photostable laser emission with good lasing efficiency was obtained. Under the demanding conditions of tightly focused transversal pumping with 532 nm, 5 mJ pulses at 10 Hz repetition rate, the commercial dye Pyrromethene 567 exhibited laser action with only a 10% drop in the laser output after 10(6) pump pulses in the same position of the sample.