Secondary, but second to none : The use of secondary alkyl halides in transition‐metal‐catalyzed cross‐coupling reactions (see scheme) has advanced significantly over the last five years. Selected examples of these transformations are examined, including mechanistic and stereochemical aspects.
Easy and direct : Regioselective Mizoroki–Heck‐coupling reactions using heteroaromatic tosylates as electrophiles were achieved, thus providing direct and easy access to highly functionalized α‐heteroarylvinyl amides and ethers.
By a flexible three‐component synthesis, alkoxy‐substituted enamides are easily available from lithiated alkoxyallenes, nitriles and carboxylic acids (see scheme). The treatment of these versatile intermediates with trifluoroacetic acid provided 5‐acetyloxazoles in moderate to good yields. Different substituents are possible at C‐2 and C‐5 and the 5‐acetyl group is a suitable handle for further synthetic transformations.
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.
Fruity electrodes : A simple bottom‐up self‐assembly method was used to fabricate rambutan‐like tin–carbon (Sn@C) nanoarchitecture (see scheme, green Sn) to improve the reversible storage of lithium in tin. The mechanism of the growth of the pear‐like hairs is explored.
Trapped in a “tea bag” : Membrane bags, fabricated from a dialysis membrane, have been employed as semipermeable containers for dendrimer‐immobilised oxazoline–copper(II) Lewis acid catalysts. Dipping them into reactant solutions leads to the catalytic conversion of the substrates, which penetrate the membrane as does the product in the reverse direction (see scheme).
H bonds make the catalysts! A single hydrogen bond between ligands coordinated to a rhodium center is critical for the formation of pure supramolecular catalysts for asymmetric hydrogenation reactions. The ester group of the amidite ligand (see scheme) also forms a hydrogen bond with the coordinated substrate. Use of the heterocomplex afforded the highest enantioselectivity reported to date for the hydrogenation of several ester substrates.
Fully loaded : Noncovalent anchoring of liposomes into polymer multilayered films with cholesterol‐modified polymers allows the preparation of capsosomes—liposome‐compartmentalized polymer capsules (see picture). A quantitative enzymatic reaction confirmed the presence of active cargo within the capsosomes and was used to determine the number of subcompartments within this novel biomedical carrier system.
