Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

Herstellung von substituierten 2-Aminooxazol-4-carbonitrilen

Preparation of Substituted 2-Aminooxazole-4-carbonitriles During our synthetic programme to convert 4-isoxazolylthioureas 3 into the corresponding carbodiimides 5 , a side reaction leading to the hitherto unknown 2-aminooxazole-4-carbonitriles 6 was observed. By selecting appropriate reaction conditions, it was possible to improve the yields of the carbodiimides 5 as well as of the novel oxazole-carbonitriles 6 at will, thus allowing the synthesis of 6 to be conducted in very good yields. To overcome the difficulty of isolating unstable carbodiimides, the synthesis of 6 is best carried out in a one-pot procedure. A limited mechanistic study showed that the formation of 6 proceeds via 5 as the only intermediate. The stability of the N?C?N bonds against base attack (depending strongly on both sterical hindrance and electronic-density factors) forms the only limitation of this new synthetic pathway to oxazole-4-carbonitriles.     

The three space problem in topological groups

We study compact, countably compact, pseudocompact, and functionally bounded sets in extensions of topological groups. A property P is said to be a three space property if, for every topological group G and a closed invariant subgroup N of G, the fact that both groups N and G/N have P implies that G also has P. It is shown that if all compact (countably compact) subsets of the groups N and G/N are metrizable, then G has the same property. However, the result cannot be extended to pseudocompact subsets, a counterexample exists under p=c. Another example shows that extensions of groups do not preserve the classes of realcompact, Dieudonné complete and μ-spaces: one can find a pseudocompact, non-compact Abelian topological group G and an infinite, closed, realcompact subgroup N of G such that G/N is compact and all functionally bounded subsets of N are finite. Several examples given in the article destroy a number of tempting conjectures about extensions of topological groups.     

Use of the Apparent Content Curves for the spectrophotometric identification of substances: identification of amphetamines

The possibility of identification of substances which have similar spectral behaviour by means of Apparent Content Curves has been studied. This study is carried out with absorption, excitation and emission spectra of several amphetamines of widespread pharmaceutical use. Results obtained show that amphetamine, phenylpropanolamine, pseudoephedrine, phenylephrine, epinephrine, dopamine and methoxyamphetamine can be identified with a probability of >95%.     

Reaction of SbPO4 with lithium in non-aqueous electrochemical cells: preliminary study and evaluation of its electrochemical performance in anodes for lithium ion batteries

SbPO₄, a phosphate with a layered structure, was tested as an electrode material for lithium cells spanning the 3.0-0.0 V range. Two main electrochemical processes were detected as extensive plateaus at ca. 1.6 and 0.7 V in galvanostatic measurements. The first process was found to be irreversible, thus excluding a potential intercalation-like mechanism for the reaction and being better interpreted as a decomposition reaction leading to the formation of elemental Sb. This precludes the use of this compound as a cathodic material for lithium cells. By contrast, the process at 0.7 V is reversible and can be ascribed to the formation of lithium-antimony alloys. The best electrochemical response was obtained by cycling the cell at a C/20 discharge rate over the voltage range 1.25-0.25 V. Under these conditions, the cell delivers an average capacity of 165 Ah/kg—a value greater than those reported for other phosphates—upon successive cycling.     

Bounded sets in topological groups and embeddings

We show that the existence of a non-metrizable compact subspace of a topological group G often implies that G contains an uncountable supersequence (a copy of the one-point compactification of an uncountable discrete space). The existence of uncountable supersequences in a topological group has a strong impact on bounded subsets of the group. For example, if a topological group G contains an uncountable supersequence and K is a closed bounded subset of G which does not contain uncountable supersequences, then any subset A of K is bounded in G?(K?A). We also show that every precompact Abelian topological group H can be embedded as a closed subgroup into a precompact Abelian topological group G such that H is bounded in G and all bounded subsets of the quotient group G/H are finite. This complements Ursul's result on closed embeddings of precompact groups to pseudocompact groups.     

Magydardiendiol,diterpenoid with a new skeleton from magydaris panacifolia (umbelliferae).

Three new diterpenoids with a substituted α-cyclogeraniol skeleton have been isolated from the umbelliferae $\text{Magydaris panacifolia}$ (Vahl) Lange, for which the names of magydar-2,13-dien-11,17-diol, $\text{1}$, magydar-2,10 (20), 13-trien-17-ol, $\text{2}$, and magydar-2,10(20), 13-trien-17-yl acetate, $\text{3}$, are proposed. The structures of these substances have been deduced from spectroscopic and chemical data.     

On the effect of montmorillonite in the curing reaction of epoxy nanocomposites

The procedure for the fabrication of epoxy-based polymer layered silicate nanocomposites is important in respect of the nanostructure that is developed. To further our understanding of this, the influence of an organically modified clay (montmorillonite, MMT) on the curing kinetics of an epoxy resin has been studied by differential scanning calorimetry. Clay loadings of 10 and 20 mass% are used, and isothermal as well as dynamic cures have been investigated. For both cure schedules the effect of the MMT is to advance the reaction. Kinetic analysis yields values for the activation energy, but shows that the reaction cannot be described simply by the usual autocatalytic equation. The glass transition of the cured nanocomposites is lower than that for the cured neat resin, a result that is attributed to homopolymerisation taking place in addition to the epoxy–amine reaction.     

Minor components with the γ-cyclogeranil geraniol skeleton from Bellardia trixago (L.) all.

Trixagol 1 and fourteen derivatives with the skeleton of γ-cyclogeranil geraniol were isolated from Bellardia trixago, the structures were determined by spectroscopic methods and confirmed by partial synthesis. Furthermore. 3,4-dihydro-γ-ionone, α-ambrinol, β-sitosterol and three flavonoids 5-O-demethyl tangeretin, 5-hydroxy auranetin and 3′-methoxy calycopterin were also isolated.     

Multivariate resolution of NMR labile signals by means of hard- and soft-modelling methods

One of the difficulties frequently encountered when studying acid–base equilibria with NMR spectroscopy is the labile behaviour of the measured signal, which hinders the application of bilinear multivariate data analysis methods. In this work, a mathematical transformation is proposed for the conversion of NMR labile signals to inert signals, which make possible the application of multivariate data analysis methods, based on bilinear data models. The procedure has been applied to the analysis of NMR data corresponding to the acid–base equilibria of nucleotides dCMP and dGMP. Both hard-modelling (EQUISPEC) and soft-modelling (MCR-ALS) approaches have been applied for the analysis and resolution of transformed bilinear NMR data matrices.