Photochemical Deracemization of 4,7-Diaza-1-isoindolinones by Unidirectional Hydrogen Atom Shuttling.

By coupling a photochemical and a thermal step, a single chiral catalyst can establish a photostationary state in which the enantiopure form of a chiral compound is favored over its racemate. Following this strategy, 3-substituted 4,7-diaza-1-isoindolones were successfully deracemized (74-98% yield, 86-99% ) employing 2.5 mol % of a photocatalyst.

Rim-brominated pillarplexes and their assembly self-sorting.

We report rim-brominated pillarplexes, new examples of functionalised supramolecular organometallic complexes (SOCs). The bromide atoms can be introduced to the established pristine ligand precursor, demonstrating late-stage diversification of our ligand platform. SC-XRD/ED-derived crystal structures of precursor and pillarplex salts are reported along with competitive assembly experiments of the Ag(I) pillarplex, showing narcissistic self-sorting behavior.

Screening Privileged Alkyl Guanidinium Motifs under Host-Mimicking Conditions Reveals a Novel Antibiotic with an Unconventional Mode of Action.

Screening large molecule libraries against pathogenic bacteria is often challenged by a low hit rate due to limited uptake, underrepresentation of antibiotic structural motifs, and assays that do not resemble the infection conditions. To address these limitations, we present a screen of a focused library of alkyl guanidinium compounds, a structural motif associated with antibiotic activity and enhanced uptake, under host-mimicking infection conditions against a panel of disease-associated bacteria. Several hit molecules were identified with activities against Gram-positive and Gram-negative bacteria, highlighting the fidelity of the general concept.

Crystal structure elucidation of a geminal and vicinal bis(trifluoromethanesulfonate) ester.

Geminal and vicinal bis(trifluoromethanesulfonate) esters are highly reactive alkylene synthons used as potent electrophiles in the macrocyclization of imidazoles and the transformation of bypyridines to diquat derivatives via nucleophilic substitution reactions. Herein we report the crystal structures of methylene (CHFOS) and ethylene bis(trifluoromethanesulfonate) (CHFOS), the first examples of a geminal and vicinal bis(trifluoromethanesulfonate) ester characterized by single-crystal X-ray diffraction (SC-XRD). With melting points slightly below ambient temperature, both reported bis(trifluoromethanesulfonate)s are air- and moisture-sensitive oils and were crystallized at 277 K to afford two-component non-merohedrally twinned crystals.

Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn, Zn, and Mixed-Valence Fe.

Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC)─the sulfur-analog of 1,4-benzenedicarboxylate (BDC)─together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Single-crystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF)] () to two-dimensional (2D) honeycomb sheets observed for [Zn(BDDTC)][Zn(DMF)(HO)] (). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe(BDDTC)(OH)] ().

Development and validation of an automated microfluidic perfusion platform for parallelized screening of compounds in vitro.

Monoamine transporters are of great interest for their role in the physiological activity of the body and their link to mental and behavioural disorders. Currently, static well-plate assays or manual perfusion systems are used to characterize the interaction of psychostimulants, antidepressants and drugs of abuse with the transporters but still suffer from significant drawbacks caused by lack of automation, for example, low reproducibility, non-comparability of results. An automated microfluidic platform was developed to address the need for more standardized procedures for cell-based assays.

Photochemical Isomerization of Cyclohept-1-ene-1-carbaldehyde: Strain-Release Cycloadditions and Ene Reactions.

Cyclohept-1-ene-1-carbaldehyde undergoes photoinduced → isomerization at λ = 350 nm. The ring strain facilitates Diels-Alder cycloaddiions with 1,3-dienes, [3 + 2] cycloadditions with 1,3-dipoles, and ene reactions with olefins. Products are -fused at the cycloheptane core and were obtained in yields of up to 82%.

Arene Activation through Iminium Ions: Product Diversity from Intramolecular Photocycloaddition Reactions.

While 2-alk-ω-enyloxy-sustituted benzaldehydes do not display any photochemical reactivity at the arene core, the respective iminium perchlorates were found to undergo efficient reactions either upon direct irradiation (λ=366 nm) or under sensitizing conditions (λ=420 nm, 2.5 mol% thioxanthen-9-one). Three pathways were found: (a) Most commonly, the reaction led to benzoxacyclic products in which the olefin in the tether underwent a formal, yet unprecedented carboformylation (13 examples, 44-99 % yield).

Boron-nitrogen substituted dihydroindeno[1,2-b]fluorene derivatives as acceptors in organic solar cells.

The electrophilic borylation of 2,5-diarylpyrazines results in the formation of boron-nitrogen doped dihydroindeno[1,2-b]fluorene which can be synthesized using standard Schlenk techniques and worked up and handled readily under atmospheric conditions. Through transmetallation via diarylzinc reagents a series of derivatives were synthesized which show broad visible to near-IR light absorption profiles that highlight the versatility of this BN substituted core for use in optoelectronic devices. The synthesis is efficient, scalable and allows for tuning through changes in substituents on the planar heterocyclic core and at boron.

Tetraacylstannanes as Long-Wavelength Visible-Light Photoinitiators with Intriguing Low Toxicity.

The first tetraacylstannanes Sn[(CO)R] (R=2,4,6-trimethylphenyl (1 a) and 2,6-dimethylphenyl (1 b)), a class of highly efficient Sn-based photoinitiators, were synthesized. The formation of these derivatives was confirmed by NMR spectroscopy, mass spectrometry, and X-ray crystallography. The UV/Vis absorption spectra of 1 a, b reveal a significant redshift of the longest wavelength absorption compared to the corresponding germanium compounds.