Economical atoms : 2‐Cyclopenten‐1‐ones, 5‐alkylidenefuran‐2(5 H)‐ones and indan‐1‐ones have been synthesized by atom‐economic reductive cyclocarbonylation of internal alkynes with carbon monoxide catalyzed by [{RhCl(CO)2}2]/CO(NH2)2 in the presence of water (see scheme).
Rhenium does the job! A readily available rhenium complex efficiently catalyzed the direct Meyer–Schuster‐like rearrangement of different alkyl‐ and aryl‐substituted propargylic secondary and tertiary alcohols to the corresponding α,β‐unsaturated compounds, which were produced with virtually complete E stereoselectivity. The reaction proceeded under neutral conditions and no racemization of potentially enolizable stereocenters was observed.
A uniform, conformal, pure copper metal thin film was grown at very low substrate temperatures (100–120 °C) on Si(100) substrates by atomic layer deposition involving the ligand exchange of [Cu(OCHMeCH2NMe2)2] with Et2Zn (see scheme). Patterned copper thin films of Cu nanotubes (diameter 150 nm, length 12 μm) were fabricated.
[2+3] Cycloadditions! The metal‐mediated [2+3] cycloaddition of acyclic [?O+N(R2)?(H)R3] and nonaromatic cyclic nitrones [?O+Na?CHCH2CH2CbMe2(Na? Cb)] to palladium‐bound isonitriles cis‐[PdCl2(C?NR)2] proceeds under mild conditions to furnish novel heterocyclic carbene complexes, which then undergo N? O bond rupture to give imino complexes and free isocyanates (see scheme).
A convenient route with high stereo control to γ‐acetoxy dienoates is provided by the reaction of methyl propiolate with aldehydes in the presence of ZnEt2 and N‐methylimidazole at room temperature, followed by the catalytic conversion of the resulting γ‐hydroxy‐α,β‐acetylenic esters with p‐N,N‐dimethylaminopyridine (DMAP) in acetic anhydride (see scheme).
A new page in the phase book : The metastable nitride β‐Ca3N2, the synthesis, crystal structure (see picture), and physical properties of which are reported, is an isotype of corundum (α‐Al2O3). Vacancies in the crystal structure of β‐Ca3N2 are discussed by using full‐potential local orbital methods and taking into account both the physical properties and the density of states.
Two members of a family of pyrrole–imidazole marine alkaloids, (+)‐dibromophakellin and the nonnatural congener (+)‐phakellin, were synthesized enantioselectively from 4‐hydroxy‐L ‐proline. The chiral aminal at C10 was constructed efficiently by means of an Overman‐type [3,3] sigmatropic rearrangement of an enamide (see scheme).
Efficient route : A novel RhI‐catalyzed regio‐ and stereospecific carbonylation reaction of (1‐alkynyl)cyclopropyl ketones by selective activation of a carbon? carbon σ bond of the cyclopropane ring was demonstrated (see scheme). This method provides a general, efficient, stereoselective route to synthesise 1,3,5‐trisubstituted and 1,3,5,6‐tetrasubstituted 5,6‐dihydrocyclopenta[c]furan‐4‐one with convertible functional groups.
Clicking iron : Cheap and environmentally friendly [Fe(OAc)2] is used for the catalysis of cycloadditions between aryl nitriles and trimethylsilyl azide to prepare substituted 1H‐tetrazoles in good yield (see scheme).
Rivaling the best one : Thermal [2+2] cycloadditions of TCNE, TCNQ, and F4‐TCNQ to N,N‐dimethylanilino‐substituted cyanoalkynes afforded a new class of organic super‐acceptors featuring efficient intramolecular charge‐transfer interactions. These acceptors rival the acceptor F4‐TCNQ in the propensity for reversible electron uptake as well as in electron affinity (see figure), which makes them interesting as p‐type dopants for potential application in optoelectronic devices.
This template will self‐destruct : A unique particle‐growth mechanism involves growth of new coordination polymers on the surface of initially formed hexagonal blocks and concomitant dissolution of the blocks to form hexagonal tubes (see scheme and scanning electron, optical, and fluorescence microscopy images). Calcination of the tubes yields ZnO particles of the same shape.
Surface‐hopping simulations are used to study the nonradiative relaxation of 9H‐guanine. Two distinct S1→S0 (ππ*→gs) decay channels, both of which pass through a conical intersection (CI), are found to be responsible for the experimentally observed double‐decay behavior (see schematic diagram).
