Grind and cure: Using the nonsteroidal anti‐inflammatory drug naproxen, a novel concept is demonstrated to dramatically enhance the rate of the recently discovered process of deracemization using abrasive grinding. The process relies on a gradual feed of the racemic target material by an in situ conversion.
In the garden of dispersion: High‐accuracy ab initio calculations are performed to determine the nature of the interactions and the most favorable geometries between CO2 and heteroaromatic molecules containing nitrogen (see figure). Dispersion forces play a key role in the stabilization of the dimer, because correlation effects represent about 50 % of the total interaction energy.
Positive discrimination : Chemo‐ and regioselective palladium‐catalyzed cycloetherification of allendiols, namely β,γ‐ and γ,δ‐allendiols, may occur by judicious choice of palladium‐catalyzed conditions owing to their potential ability to discriminate between both nucleophilic sites (see scheme).
Pressing the configurational switch : Use of enantiomeric Ir catalysts allows the vinylpiperidine building blocks 2 a and 2 b to be synthesized with high selectivity. Total syntheses of the dendrobate alkaloid (+)‐241 D, its C6‐epimer, and a spruce alkaloid are presented as applications.
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.
Chain change : Variations in the position, number, and chain length of the n‐alkoxy chains readily tune the liquid‐crystalline properties of 2,5‐diaryl‐1,3,4‐thiadiazole derivatives from smectic to hexagonal columnar mesophases at room temperature. The calamitic S‐heterocyclic compounds show electrical conductivity in both solid and liquid‐crystal states.
Losing the grip : The synthesis of multivalent low‐molecular‐weight dendrons with lysine branching units coupled to disulfide‐linked spermine surface groups is described. It is furthermore demonstrated that the dendrons bind DNA with good affinity (see image), but are also able to release the DNA in a reductive environment.
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.
Molecular switches : Highly efficient acido‐ and photoswitchable frequency doublers (see scheme) based on the indolinooxazolidine core are studied by means of hyper‐Rayleigh experiments and quantum‐chemical calculations.
From blue to red: While four π‐conjugated nitrophenolates absorb within a relatively narrow region in solution, they cover the entire visible spectrum when isolated in vacuo (see picture). The work combines gas‐ and solution‐phase spectroscopy and provides the first benchmark of theoretical excitation energies for nitrophenolates.
Gold and rings : The gold(I)‐catalyzed addition of aldehydes to 1,6‐enynes gives 1,3‐dienes, by a cycloaddition/fragmentation process. 1,5‐Enynes react with aldehydes and ketones by the 5‐endo‐dig pathway to give the corresponding cycloadducts.
Free to decide : Various 4‐(α‐styryl) γ‐lactams are synthesized in 61–88 % yield by a phosphine‐free palladium‐catalyzed carbopalladation/allylic alkylation domino sequence (see scheme). The cyclization is totally regio‐ and diastereoselective in favor of the 3,4‐trans‐disubstituted γ‐lactam. The process is successfully applied to the synthesis of a new aza analogue of the naturally occurring lignan (+)‐oxo‐parabenzlactone.
The natural way : A sensitive NMR spectroscopic method is developed to obtain well‐resolved two‐dimensional spectra (15N–1H and 13C–1H) for natural‐abundance (that is, without the need for isotopic enrichment) large‐molecule samples, such as biopharmaceuticals. This method gives structural insights on two lyophilized aprotinin samples and three insulin samples in lyophilized, microcrystalline suspension formulation (red; see picture) and fibril (green) forms.
The stereogenic centers at C3 and C12 of meloscine ( 3 ) can be established in the photochemical key step 1 → 2 . 1,2‐retro‐Benzilic acid rearrangement to a five‐membered ring, reductive amination, Claisen rearrangement, and ring‐closing metathesis are further key steps in the transformation of cyclobutane 2 into the target molecule 3 (14 steps, 9 % overall yield). Enantioselective access to (+)‐meloscine was possible when the [2+2]‐photocycloaddition was conducted in the presence of a chiral template.
