Angewandte Chemie最新文献

In the Research Article (e18505), Fumitaka Ishiwari, Akinori Saeki, and co-workers report homochiral bifacial non-fullerene acceptors (NFAs) enabling spin-selective transport in bulk-heterojunction layers, thereby suppressing recombination and boosting efficiency. Mirrored hands symbolize the enantiomeric NFAs and their opposite spin preference, shown with OPV stacks. Art by F. Ishiwari.

Single-atom catalysts (SACs) represent a pinnacle of atomic efficiency and catalytic precision. Their remarkable activity and selectivity arise from isolated, low-coordinate metal centers that engage directly in bond-forming events. However, under realistic reaction conditions, SACs are far from static. Increasing evidence reveals that single atoms undergo dynamic evolution over the reaction time. In this perspective, we challenge the conventional dichotomy that views SACs and nanoparticles (NPs) as fundamentally distinct catalytic systems. We propose that NPs, rather than acting as parallel or cooperative catalysts, may function as catalytic poisonants for SACs by trapping active metal atoms. This transformation results in loss of activity, reduced selectivity, and degradation of the catalytic system. Drawing on mechanistic studies, thermodynamic data, and experimental observations across diverse reaction classes, including hydrogenation, oxidation, and cross-coupling, we show that the aggregation of SACs into NPs is not merely a side process but rather a limitation to their stability and utility. We further outline thermodynamic and kinetic strategies to suppress this deactivation pathway and propose design principles that elevate NP suppression from a synthetic challenge to a foundational criterion in catalyst development. This perspective reframes the SAC–NP relationship as a dynamic continuum and emphasizes the importance of stabilizing isolated active sites in next-generation catalytic technologies.

In their Research Article (e202518973), Xing Guo, Lijuan Jiao, Yi Xiao, Erhong Hao, and co-workers have synthesized and described a brand-new class of spirocyclic BODIPY molecules. This research pushes the boundaries of BODIPY science and unlocks its potential for super-resolution fluorescence imaging.

Herein we report the decarboxylative cross-coupling of tertiary benzylic carboxylic acids and aryl bromides to furnish all-carbon diaryl quaternary centers. For the first time, tertiary benzylic radicals are introduced as viable participants in metallaphotoredox-catalyzed cross-couplings by suppressing undesired benzylic radical dimerization via fast radical trapping with Cu. We demonstrate the functionalization of feedstock carboxylic acids as well as late-stage functionalization of carboxylic acid-containing drugs.

Herein we report the decarboxylative cross-coupling of tertiary benzylic carboxylic acids and aryl bromides to furnish all-carbon diaryl quaternary centers. For the first time, tertiary benzylic radicals are introduced as viable participants in metallaphotoredox-catalyzed cross-couplings by suppressing undesired benzylic radical dimerization via fast radical trapping with Cu. We demonstrate the functionalization of feedstock carboxylic acids as well as late-stage functionalization of carboxylic acid-containing drugs.

The unique potential of marine polyhydroxylated macrolides in chemical biology and drug discovery has long been constrained by their structural complexity and limited material availability, frustrating efforts in stereochemical assignment, synthesis, and mechanism-of-action elucidation. Here, we establish an integrated workflow, combining chemogenomic profiling, ultra-high-resolution NMR, and modular total synthesis, for the comprehensive functional and structural interrogation of this challenging natural product class. Applying this approach to caylobolides, natural products isolated from scarce samples of Okeania sp., we performed structure-activity relationship studies revealing that acetylation at C29 markedly reduces both cytotoxicity and antifungal activity, pinpointing a key pharmacophore. Mechanistic profiling suggests that these macrolides disrupt membrane integrity, similar to amantelide A. Using natural compound samples, we simultaneously revised the structure of caylobolide B through ¹H, 1D-selective TOCSY and HSQC NMR, and developed a modular fragment-based synthesis of these compounds. By providing a unified methodology for genetic sensitivity profiling, precise structure and stereochemistry determination, and modular total synthesis, this work unlocks new opportunities for the discovery and rational design of potent marine-derived therapeutics.

The cover represents the application of modern tools and well-suited methodology to watch photochemistry happen in real time. The approach to the photoisomerization kinetics presented in the Research Article (e202514591), Jakub Drapała, Radosław Kamiński, and co-workers, is applicable to a wide range of dithienylethene photoswitches (depicted inside the lens), undergoing reversible light-induced ring-closing/-opening reactions of various nature.

Emissions from the chemical industry, both for energy and use of raw materials, account for approximately 6% of man-made greenhouse gas emissions. In order to keep global warming at acceptable levels, these emissions—as all other emissions—have to be drastically reduced. One way to do this is the elimination of fossil feedstock from chemical production and meeting the energy demand from renewable resources. This contribution shows that the essential elements are already available at scale to provide C₁-building blocks, olefins, aromatics, and ammonia as the key base chemicals. Methanol can be produced from CO₂ and renewable hydrogen, olefins from the methanol-to-olefins and related processes, for aromatics, the methanol-to-aromatics process is available, supplemented by biomass and recycled polymers as feedstock, and also for ammonia process concepts with a strongly reduced greenhouse gas footprint are available. Current hurdles are the partly unattractive economic boundary conditions and the rate at which a change in the feedstock situation can be achieved. Moreover, high amounts of renewable energy are required, which accounts for about half of the current global electricity production.

Pseudotetraivprolid ist ein neuer Akteur unter den Detoxin/Rimosamid-ähnlichen Naturstoffen. Die Biosynthese erfordert FabD aus dem Primärstoffwechsel und einen PipDFG-Komplex für die Acetylierung im letzten Schritt – wodurch schließlich die anti-antibiotische Wirkung entsteht.

Pseudotetraivprolid ist ein neuer Akteur unter den Detoxin/Rimosamid-ähnlichen Naturstoffen. Die Biosynthese erfordert FabD aus dem Primärstoffwechsel und einen PipDFG-Komplex für die Acetylierung im letzten Schritt – wodurch schließlich die anti-antibiotische Wirkung entsteht.