A boost from the branches : Incorporation of the dithieno[3,2‐b:2′,3′‐d]phosphole system as a core in oligo(phenylenevinylene) dendrimers (an example is shown here) provides materials that exhibit energy‐transfer features relaying incoming photons from the dendrons towards the core, which in turn shows enhanced emission intensity. The optical properties and self‐assembly features of the dendrimers can be impacted by the terminal groups (‐H, ‐CF3, or ‐NPh2) employed.
Ligand design by‐pam : A ruthenium‐catalyzed asymmetric arylation of aldehydes with arylboronic acids has been developed, giving chiral diarylmethanols in good yields. The use of a chiral bidentate phosphoramidite ligand ((R,R)‐Me‐bipam) led to excellent enantioselectivities.
Caught on film : A semitransparent and intensely luminescent monolayer film of oriented Gd2O3:0.05 Eu platelet crystallites is fabricated by annealing the precursor hydroxide film (see scheme). The photoluminescence properties of the as‐transformed film are greatly improved over those of the hydroxide film, and are much more pronounced than those of the corresponding Gd2O3:0.05 Eu powder.
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).
Number of members makes a difference : The [2+2+2] intramolecular cyclotrimerisation of a new series of 20‐ and 25‐membered azamacrocycles catalysed by the Wilkinson's catalyst are reported (see scheme). The 20‐ and 25‐membered azamacrocycles show different reactivity. Why? Theoretical calculations give insight into the reactivity differences observed for the 20‐ and 25‐membered macrocycles.
Cutting ties : Strand scission and base release in hydroxy‐radical adducts of 3′‐uridine monophosphate (UMP) have been explored by using density functional theory. The presence of the ribose 2′‐OH group and the resultant formation of low‐barrier hydrogen bonds with oxygen atoms of the 3′‐phosphate linkage are highly important for hydrogen transfer and the subsequent bond‐breakage reactions (see picture).
Economical approach : The first organocatalytic asymmetric intramolecular hydroarylation of phenol‐ and aniline‐derived enals offers one of the most straightforward and atom‐economic approaches to enantioriched chromans and tetrahydroquinolines (up to 96 % ee; see scheme).
Aerial pingpong : The lithium acetate enolate anion, the prototypical lithium salt of an α‐deprotonated carboxylate, was prepared in the gas phase by electrospray ionization (ESI) and collision‐induced ionization (CID). Its structure, reactivity, and energetics are presented along with the results of high‐level computations.
Cascade reactions : Lewis acid catalyzed cascade reactions of 1,6‐diynes and 1,6‐enynes with arylvinylidenecyclopropanes produce polycyclic compounds and isopropylidene‐3,3‐diarylcyclobut‐1‐enylmethyl derivatives (see scheme) in good to high yields along with a PtCl2‐catalyzed cyclization and a Cu(OAc)2 ? H2O‐catalyzed Eglinton coupling reaction.
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).
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).
Expanded porphyrins : The electronic excited states of two forms of meso‐hexakis(pentafluorophenyl)‐substituted gold(III) hexaphyrin(1.1.1.1.1.1), such as that depicted, have been investigated by density functional calculations and magnetic circular dichroism spectroscopy to assign their low‐energy excited singlet states.
PS, I love you! Novel mixed phosphole/thiophene π‐conjugated systems were synthesized and their electronic properties have been studied both experimentally by UV/Vis spectroscopy and electrochemistry and by theoretical calculations. Exploiting the chemistry of both P‐ and S‐heteroles allows the generation of a diverse range of novel ring‐fused benzophosphole–thiophene derivatives.
Molecular versatility : Unusual reactivities such as hydrolysis, nucleophilic aromatic substitution, and addition reactions of human orotidine‐5′‐monophosphate decarboxylase are explained by crystal structures and involve a nucleophilic lysine residue that normally is expected to act solely as a general base (RP=phosphoribosyl, R=CO2H, CN, acetyl, N3, I; R′=OH, SH, acetyl, hydroxymethyl).
