Potential immunosuppressive agents : Candelalides A, B and C (see figure), novel blockers of the voltage‐gated potassium channel Kv1.3, have been efficiently synthesized for the first time in a convergent and unified manner starting from (+)‐5‐methyl‐Wieland–Miescher ketone. The method explored has potential for preparing various types of candelalide analogues for the structure–activity relationship studies.
Do the twist : The reaction of in situ generated phosphinidenes with phosphaalkynes is a facile route to the new metal‐coordinated η3‐diphosphavinylcarbene 1 , which shows facile ligand‐exchange reactions and undergoes an unprecedented rearrangement that involves phosphinidene complex 2 and η3‐phosphaalkenylphosphinidene complex 3 , the 1,3 isomer of 1 .
Supra‐mega ion pairing : Multicationic organoruthenium dendrimers show a notable tendency to self‐aggregate when the concentration is increased, leading to megamers. This tendency increases with the generation. The self‐aggregation of dendrimers to megamers is coupled with a decrease in the extent of ion pairing, as illustrated.
A practical and sustainable chemical process for the synthesis of highly substituted aldol?lactol products was achieved for the first time through the asymmetric Barbas–List aldol (BLA) reaction of 2‐hydroxybenzaldehydes with acetone in the presence of a catalytic amount of trans‐4‐OH‐L ‐proline (see scheme).
Protein roll call : Peptide‐based building blocks, in which both an α‐helix‐forming segment and a β‐sheet segment are located within a single macrocyclic structure, self‐assemble into α‐helix‐decorated artificial proteins. This approach provides a starting point for developing artificial proteins that can modulate α‐helix‐mediated interactions occurring in a multivalent fashion.
Aryl–alkyl cross‐coupling products are obtained by the iron‐catalyzed oxidative heterocoupling of organozinc reagents under mild conditions. This novel reaction pathway is versatile, allowing for the use of primary and secondary aliphatic diorganozinc reagents as coupling partners as well as tolerating functionalized aryl‐ and alkylzinc reagents.
Tungsten tryst : A 4‐H‐butatrienylidene complex of tungsten was successfully isolated and structurally characterized. It undergoes a unique self‐coupling, which leads to a dimer (see picture; P pink, O red) with a cross‐conjugated π system and with electrochemically and magnetically active metal centers.
Silica supports : Well‐defined silica‐supported Mo–alkylidene complexes containing one alkoxy/aryloxy substituent are selectively obtained by grafting onto silica either well‐defined molecular bis(alkoxy) or alkoxyamido complexes (see scheme). These silica‐supported complexes are highly efficient catalyst precursors for the metathesis of acyclic alkenes. However, they display poor performances in ring‐closing metathesis reactions, possibly due to the relatively large siloxy ligand (silica) inducing a greater rigidity.
Curvy ligands for H 2 storage? Enhancement of H2 adsorption has been observed in coordination framework materials, an example of which is depicted, by the introduction of phenanthrene and 9,10‐dihydrophenanthrene groups into porous CuII–carboxylate framework materials of NbO topology.
A sustainable method for the fabrication of metallic surfaces with flower‐like fractal morphology was developed by using a three‐dimensional supramolecular assembly as a template. Modifying Au nanoflakes with self‐assembled monolayers or polymers allows the surface wettability to be adjusted from superhydrophobic to superhydrophilic (see figure). Furthermore, Au nanoflakes present excellent substrates for surface‐enhanced Raman spectroscopy (SERS).
Efficient and general conditions for the formation of stereodefined trisubstituted alkenes by using the rhodium‐catalyzed reaction of unactivated Baylis–Hillman adducts with either organoboronic acids or potassium trifluoro(organo)borates are reported (see scheme).
The aggregation and self‐assembly of square‐planar alkynylplatinum(II) complexes is induced by the use of a chiral polyacetylene with a helical conformation (see scheme). The chain helicity of the chiral polyacetylene under basic conditions has also been demonstrated to be enhanced by the presence of the positively charged platinum(II) complexes.
Fast moving : A new pentad (see figure) composed of silicon phthalocyanine (SiPc), as electron donor, that is connected with two units of naphthalenediimide (NDI) and fullerene C60, as electron acceptors, undergoes fast and efficient charge‐separation processes via the NDI and SiPc singlet excited states.
Taxing taxanes : A new method for the preparation of alk‐2‐ene‐1,4‐diols from 1,3‐dienes, especially for geometrical constrained derivatives, via dioxirane derivative formation followed by TiIII‐induced oxirane ring opening, is described. The strategy has been very efficiently implemented to the construction of the 11‐ene‐10,13‐diol moiety present in taxol derivatives.
A DNA spin‐off : Electrospinning of DNA complexes gives nanofibers with a highly ordered morphology that allows homogeneous distribution of encapsulated multiple chromophores. The emission color can be controlled by suitable choice of the donor–acceptor pair and the doping ratio. Pure white‐light emission from nanofibers is demonstrated (see picture).
