Perrhenat-katalysierte Umlagerung von Ethinyl-β-ionol

Perrhenate-Catalyzed Rearrangement of Ethinyl-β-ionol The rearrangement of 2-ethinyl-β-ionol ( 1 ) to α,β-unsaturated carbonyl compounds using tetraalkylammonium perrhenate catalysts was studied. It was found that the Rupe-Kambli product, ketone 2 , is the main product (ca. 70%) of this rearrangement. The by-product 4 (ca. 15%) is formed in a ring-closure reaction.     

First enantioselective allylic etherification with phenols catalyzed by chiral ruthenium bisoxazoline complexes

Regio- and enantioselective substitution of cinnamyl chloride by phenols has been achieved with up to 82% enantiomeric excess, using a ruthenium catalyst prepared from [Cp*(CH(3)CN)(3)Ru][PF(6)] and a chiral bisoxazoline ligand.     

Fluorescence lifetimes and emission patterns probe the 3D orientation of the emitting chromophore in a multichromophoric system

In this Communication, we report on the fluorescence behavior of an individual first generation multichromophoric dendrimer. The fact that each of the chromophores in time acts as a fluorescent trap is demonstrated by directly probing the dipole orientation of the emitting chromophore by means of defocused wide-field imaging and comparing experimental and calculated emission patterns. It is shown that in such cases the electromagnetic boundary condition effect results in discrete changes in the fluorescence lifetime as a function of time for individual dendrimers.     

Segment dynamics in thin polystyrene films probed by single-molecule optics

Single fluorescent molecules (represented by spheres with a volume equal to the actual van der Waals volume of the molecule) has been embedded in a polystyrene matrix (left). Such molecules act as probes for the study of polymer nanoscale (segmental scale) dynamics in thin films deposited on a glass cover slide (right).     

Precise structure activity relationships in asymmetric catalysis using carbohydrate scaffolds to allow ready fine tuning: dialkylzinc-aldehyde additions

The ready construction of 24 stereochemically and functionally diverse carbohydrate ligand structures from a core D-glucosamine scaffold has allowed the evaluation of broad ranging structure activity relationships in ligand accelerated zincate additions to aldehydes, with variations in deltadeltaG+/+(R-S) of up to 5650 J mol(-1) that create opposing senses of asymmetric induction and that are consistent with models based on several ligand X-ray structures and molecular mechanics analysis. Factorial analysis of enantioselectivity using key dihedral angles and steric volume on N-2 also highlight the potential for the use of factorial design in ligand construction.     

The indecomposable representation of SO0(2, 2) on the one-particle space of the massless field in 1 + 1 dimension

In the continuum O(3) sigma model in two spatial dimensions, there are topological solitons whose size can be stabilized by adding Skyrme and potential terms. This Letter describes a lattice version, namely a natural way of modifying the 2D Heisenberg model to achieve topological stability on the lattice.     

Chain mechanisms for the dehydro-bromination of ring-substituted α-bromoacetophenones in alcohols

Ring substituted α-bromoacetophenones undergo efficient photodecomposition upon ultraviolet irradiation in alcohol solvents. The process involves chain reactions mediated by the ketyl radicals derived by hydrogen abstraction from the alcohols. It is suggested that two chain reactions involving hydrogen and electron transfer may be taking place concurrently. Competitive studies lead to relative rate constants for the reactions of ketyl radicals with ring-substituted α-bromoacetophenones.