Panacea for aldol desymmetrizations : We describe an easy entry for the desymmetrization of 4‐substituted‐cyclohexanones catalyzed by proline, using as cocatalysts different hydrogen‐bonding donors (see scheme), which dramatically improves the catalytic efficiency of proline in desymmetrization reactions.
Rings around a ring : The synthesis, characterization, material properties and biological studies of novel hexakis porphyrinato cyclotriphosphazene systems (see scheme) and their metal derivatives are described.
To be or not to be solvated is the decisive parameter that controls the photoinduced hydrogen‐atom transfer in diastereomeric ketone/phenol dyads. A kinetic solvent effect that refers to hydrogen bonding between the phenol and the solvent is suggested to be the main source of the stereoselective discrimination in the hydrogen transfer (see figure).
Stable ligation : A series of dendritic porphyrins, such as that depicted in which benzyl ether dendrons were linked to a porphyrin core through 1,2,3‐triazole links, was synthesized. Absorption and fluorescence spectra showed a stable axial ligation at the zinc center of the porphyrin core by triazole links in dendritic wedges and indicated that the position of the triazole links strongly affected the stability of the axial ligation within the dendrimer.
A black whole : The black insoluble biopolymer eumelanin is prepared through the oxidative polymerization of 5,6‐dihydroxyindoles (see scheme). It has a largely unknown heterogeneous structure and unique optoelectronic properties. Current structural models are presented and possible applications are discussed.
The Midas touch : The low‐temperature transformation of methanol to methyl formate, formaldehyde, and formic acid is promoted by atomic oxygen adsorbed on metallic gold (see picture). The reactions occur with O‐containing Au nanoparticles formed on Au(111) upon oxidation with ozone at 200 K; the facile esterification to methyl formate occurs well below room temperature.
New Pd ‐ and Pt‐biscarbenes : The synthesis by the stoichiometric transmetalation reactions from Fischer alkoxy‐chromium(0) carbene complexes of stable mononuclear (palladium and platinum) alkoxy‐biscarbene complexes is reported. The structure, bonding situation, and the electronic and redox properties of these complexes are studied by a combination of experimental and computational (DFT) methods.
A designer monomeric protein with a βαβ fold—two parallel β strands connected by an α helix (see structure)—was constructed solely from coded amino acids. The high thermal stability of the structure is due to a large extent to tryptophan–tryptophan interactions between the two β strands.
One Heck of a reaction : Treatment of arylboronic acids or aryltrifluoroborates with vinyl acetate by using a palladium(II) catalyst gives the corresponding styrenes (see scheme). No palladium reoxidant is needed and the vinylation is performed under non‐inert conditions
Many components make light work : A novel synthetic strategy for the preparation of pyridines and isoquinolines in high chemo‐ and regioselectivity has been developed. By manipulating the reaction conditions, either product can be generated smoothly in a highly efficient and atom‐economic manner (see scheme).
Works without ruthenium as well : Dye‐sensitized solar cells (DSSCs) incorporating metal‐free organic dyes have been considerably improved in recent years. Various design strategies have been established and are employed successfully in the synthesis of novel sensitizers. In this Review, structure–property–efficiency correlations are deduced from a vast number of dyes, which should help to design new and highly efficient sensitizers.
Two‐faced nanocrystals : Rapid addition of a second aliquot of silver nitrate during a polyol synthesis led to the formation of anisotropically truncated octahedrons as a result of oxidative etching and overgrowth of silver nanocubes. Three adjacent faces of the nanocube grew more rapidly than the three other faces, generating a non‐centrosymmetric structure (see picture).
