Diastereoselective total synthesis of (+)-13-stemarene by fourth generation methods: a formal total synthesis of (+)-18-deoxystemarin

The problem of constructing diastereoselectively the C/D ring system of stemarane diterpenes from a bicyclo[2.2.2]octane intermediate was solved resulting in very simple synthesis of (+)-13-stemarene 1. The obtaining of the latter represents also a formal synthesis of (+)-18-deoxystemarin 2. In the key step, the epimeric mixture 10, dissolved in toluene, was converted by the action of TsOH into (+)-stemar-13-en-15-one 28.     

Hydrogen-bond-mediated self-assembly of 26-membered diaza tetraester crowns of 3,5-disubstituted 1H-pyrazole. Dimerization study in the solid state and in CDCl3 solution

By using an improved synthetic method reported earlier, the cyclic stannoxanes obtained from RN-diethanolamine (R = Me, Bu) and dibutyltin oxide have been reacted with 1H-pyrazole-3,5-dicarbonyl dichloride to afford 26-membered diaza tetraester crowns (1, R = Me; 3, R = Bu) and 39-membered triaza hexaester crowns (2, R = Me; 4, R = Bu). The new structures were identified from their analytical and spectroscopic ((1)H and (13)C NMR, FAB-MS, and/or ESI-MS) data. Both diaza tetraester crowns (1 and 3), containing two 1H-pyrazole units, self-assemble into dimeric species through the formation of four hydrogen bonds involving the two NH pyrazole groups and the two tertiary amine groups of both crowns, as proved by X-ray crystallography and NMR analysis. Preliminary NMR, ESI-MS, MALDI-TOF-MS, and molecular modeling studies suggest that, in CDCl(3) solution, 1 interacts with ethyleneurea (ETU), affording 1:1, 2:1, and 2:2 1-ETU complexes.     

Organocatalytic enantioselective (3+2) cycloaddition using stable azomethine ylides

We have developed a highly efficient procedure for carrying out the catalytic enantioselective (3+2) cycloaddition between enals and stable azomethine ylides such as isoquinolinium and phthalizinium methylides. Under the optimized reaction conditions highly substituted chiral pyrroloisoquinolines and pyrrolophthalazines have been obtained in high yields and excellent diastereo- and enantioselectivities.     

Solid-State 1H-NMR Relaxation Properties of the Fruit of a Wild Relative of Eggplant at Different Proton Larmor Frequencies

¹H longitudinal relaxation time profiles (T1) at different proton Larmor frequencies were registered for a solid-state plant tissue by using fast field cycling (FFC) nuclear magnetic resonance (NMR) spectroscopy. T1 distributions were obtained and the curves deconvoluted in order to differentiate among the different T1 components. Among the components, two were assigned to hydrophobic (e.g., fatty acid) and hydrophilic (e.g., saccharide) molecular systems, whereas the others were attributed to bulk and bound water. This paper shows for the first time solid-state FFC-NMR spectroscopy applied to plant tissue and reveals that relaxometry is a very promising technique for studying plant systems.     

On the importance of specific solvent effects in electron trransfer reactions

The intramolecular electron transfer reaction within the binuclear complex formed between tetraamminepyrazinecarboxylatocobalt(III) and aquopentacyanoferrate(II) ions is studied in various binary aqueous media at different temperatures. Results could not be explained on the basis of a primitive model. Experimental data were fitted by using a multiparameter regression which shows the important role played by specific interactions on reactivity. © 1993 John Wiley & Sons, Inc.     

Reassignment of the Configuration of Several Keto-cyclolignans Prepared from Podophyllotoxin

The configuration of several keto-cyclolignans related to podophyllotoxin has been reviewed. Under basic catalysis, the configuration at the C-atom in α-position to the lactone carbonyl group in podophyllotoxone is inverted instead of the C-atom in α-position to the ketone group, as it has been reported.     

UV-visible spectroscopic and electrochemical study of the complex formation between Fe(II) and 5-amino-1,10-phenantroline (5-Aphen) in aqueous solution

The system Fe(II)-5-Aphen-H₂O was studied. The spectroscopic and electrochemical results show that only one stable complex between Fe(II) and 5-Aphen forms, having a 1:3 stoichiometric ratio. The spectrophotometry study allowed determination of the formation constant of the complex (log β₃ = 23.42 ± 0.06). Also, the stability of the complex was evaluated as a function of pH; it was found that it decomposed at low pH values depending on the concentration and a pseudo-first order kinetics constant associated with k′ = 0.011 min⁻¹. The results are in agreement with the electrochemical behaviour observed in the system, which indicated that at pH 1.33 the destruction of the complex [Fe(5-Aphen)3]²⁺ took place as a function of time; however, when the experiments were carried out at pH 6.19 the complex was stable. The thermodynamic data obtained through the use of MEDUSA allowed construction of predominance zone diagrams of the system Fe(II)-5-Aphen-H₂O under the experimental conditions used. The thermodynamic results represented in the PZD describe the experimental behaviour reported in this work.     

Unsharp quantum logics

The event-structure of a state-event system, containing unsharp elements, can be described either as aregular involutive bounded poset, or alternatively as anunsharp orthoalgebra (called alsodifference poset oreffect algebra). Such structures give rise to different forms ofunsharp quantum logics.