The right path : The mechanism of organocatalyzed Michael addition between propanal and methyl vinyl ketone is investigated using the density functional and ab intio methods. The kinetic preference for the formation of key intermediates is established in an effort to identify the competing pathways associated with the reaction. The effect of co‐catalyst/protic solvent on the energetics of the reaction is also studied
Site creation : Enantioselective artificial metalloenzymes have been created by grafting a new active site onto bovine pancreatic polypeptide through the introduction of an amino acid capable of coordinating a copper(II) ion. This hybrid catalyst gave good enantioselectivities in the Diels–Alder and Michael addition reactions in water (see scheme) and displayed a very high substrate selectivity.
Kept in the dark : The non‐photocatalytic generation of free radicals from fine and ultrafine TiO2 particles has been studied by means of a spin‐trapping/ESR spectroscopy technique (see figure). The amount and kind of free radicals generated depends on the crystalline structure, but not on the particle dimensions.
A drug of two halves : New artificial compounds composed of a macrosphelide core skeleton and an epothilone side chain were designed and synthesized. These compounds were more potent inducers of apoptosis than the parent natural‐type macrosphelides.
Two birds with one auric stone : The title system acts as a highly efficient heterogeneous catalyst for the one‐pot tandem synthesis of imines or oximes from alcohols and the corresponding amines under mild conditions (see scheme; HAP= hydroxyapatite).
Full metal bonding : The reduction of a six‐coordinate, mononuclear Werner‐type iron(II) complex (see scheme) resulted in the isolation of a compound with an extraordinarily rare, unsupported Fe–Fe bond having an experimental Fe–Fe distance of 2.6869(6) Å and a calculated bond order of 0.5.
