Catalytic asymmetric vinylogous hydroxylation remains a largely uncharted transformation. This limitation mainly arises from two inherent obstacles: selectivity issues (regio- and enantioselectivities) and the oxidative reactivity of common oxygen donors, both of which severely compromise overall catalytic efficiency. Against this backdrop, we herein disclose a novel synthetic route enabled by copper catalysis. The procedure proceeds through an enantioselective vinylogous nitroso aldol addition, followed by copper-mediated cleavage of the N-O bond. This unified protocol provides a general, efficient approach to enantioenriched gamma-hydroxy-alpha,beta-(E)-unsaturated carbonyl scaffolds, tolerating a wide range of alkyl substrates decorated with diverse functional substituents. Mechanistically, a critical reaction intermediate was isolated and fully characterized via HRMS, 1H NMR, and 13C NMR spectroscopy. These unambiguous spectroscopic data firmly corroborate a stepwise reaction manifold, including initial C-O bond formation and subsequent N-O bond fragmentation. The synthetic practicability of our method is underscored by its implementation in the asymmetric formal syntheses of four bioactive natural products, including (+)-alpha-conhydrine, botcinin E, botcinin F, and (-)-kunstleramide. Finally, four downstream derivatizations of the target products further demonstrate the broad synthetic versatility of this copper-catalyzed vinylogous hydroxylation strategy.

Per-and polyfluoroalkyl substances (PFAS) are persistent environmental pollutants, but they also represent a fluorine-rich reservoir, making fluoride recovery from PFAS an attractive and sustainable approach to fluorine reuse. However, methods that enable scalable and high-fluoride recovery from PFAS remain scarce. Here, we report an Et3N-enabled electrochemical strategy for PFAS degradation and fluoride recovery under mild conditions. The introduction of Et3N plays a central role in the system, enabling nearly complete defluorination with high fluoride recovery. In addition, Et3N significantly reduces the sensitivity of the reaction to air and moisture, allowing for simple operation, and it can be readily scaled to the 100 g level. The recovered fluoride can be isolated as LiF, NaF, and KF, and reused in downstream fluorination reactions. These findings establish a practical and scalable electrochemical platform for converting PFAS into synthetically useful fluorine reagents.

Fluorinated alkene-containing molecules are of growing importance in pharmaceutical and agrochemical applications. Herein, we describe a copper-mediated defluorinative coupling of TMSCF2CN with diazo compounds under mild conditions, providing straightforward access to highly E/Z-selective cyanofluoroalkenes. This method features broad functional group compatibility and is amenable to the late-stage functionalization of complex molecules. Furthermore, the presence of the cyano group offers a versatile handle for further derivatization of the resulting cyanofluoroalkene products.

The pursuit of cost-effective catalysts for alkene hydrosilylation has driven extensive research in this field. However, internal alkenes remain a formidable substrate class due to their inherent thermodynamic stability, steric congestion, and poor regiocontrol in the addition reactions. This review summarizes recent advances in the hydrosilylation of internal alkenes, systematically organized by substrate type: ring-strained, heteroatom-substituted, aryl-alkyl substituted, and unactivated dialkyl alkenes. The distinct reactivity patterns and the selectivity control mechanisms for each substrate class are discussed, along with representative applications in natural product synthesis and materials science. Progress, unresolved challenges, and future directions in this vibrant field are presented, with the goal of providing readers with a foundational understanding that guides the rational design of next-generation catalysts for internal alkene hydrosilylation.

An oxalohydrazide derived from 2,7-di-tert-butylcarbazole was identified as a highly effective ligand in the copper-catalyzed coupling of (hetero)aryl chlorides with aqueous ammonia. This system enables the reaction to proceed smoothly with a catalyst loading as low as 0.1 mol % at 120 degrees C-the lowest loading ever reported for such metal-catalyzed transformations. The same catalytic system also allows coupling of (hetero)aryl chlorides at 80 degrees C and (hetero)aryl bromides at room temperature, each representing the lowest temperatures yet achieved for these coupling reactions.

Rheumatoid arthritis (RA) is a debilitating autoimmune disease characterized by persistent synovial hyperplasia, severe oxidative stress, and progressive biomechanical destruction of articular cartilage. Current pharmacological interventions predominantly rely on systemic immunosuppression, which fails to address localized mechanical wear and suffers from rapid intra-articular clearance and off-target toxicity. Herein, we present a unified biological and materials-science strategy by engineering an intelligent, stimuli-responsive hydrogel composite (CS-RB/DiOH) that simultaneously restores joint tribology and modulates lipid metabolism. Through comprehensive chemical profiling, we identified 9,10-dihydroxyoctadecanoic acid (9,10-DiOH) as a core bioactive lipid mediator. Integrated multi-omics analyses reveal that 9,10-DiOH engages ferredoxin 1 (FDX1)-dependent cuproptosis, thereby suppressing NF-kB and MAPK inflammatory signaling, inhibiting osteoclastogenesis, and attenuating synovial fibroblast hyperproliferation. To overcome delivery barriers, 9,10-DiOH is conjugated into a chitosan-based polymeric network via dynamic covalent boronate ester bonds. This architecture enables RGDmediated active targeting and temperature-, reactive oxygen species (ROS)-, and pH-triggered precision drug release. Crucially, the exposure of the lipid's hydrophobic alkyl chains at the interface provides robust biomimetic boundary lubrication, reducing the intra-articular coefficient of friction. In a murine RA model, this localized depot effectively alleviates synovitis, attenuates bone erosion, and helps preserve joint architecture. This work highlights a mechanism-driven therapeutic paradigm that synergizes metabolic cuproptosis induction with tribological restoration for comprehensive RA management.

This study investigates the performance of terphenyl phosphine palladium catalyst precursors in C-N coupling reactions of secondary aliphatic amines. The TRuPhos-based palladium catalyst precursor has been found to be highly efficient, combined with NaOTMS as base, especially for the C & horbar;N coupling of five-membered heteroaryl halides with cyclic secondary aliphatic amines (including alpha-branched, sterically hindered amines) as well as acyclic aliphatic amines. Replacing the 2,6-isopropyl groups on the non-phosphorus-containing phenyl ring with sterically less demanding isopropoxy groups is a key reason why TRuPhos is highly efficient for the C & horbar;N coupling of bulky secondary aliphatic amines, whereas the presence or absence of an isopropyl group at the 4-position of this phenyl ring has little effect on the catalytic performance. Mechanistic studies reveal that with NaOTMS as the base, the transmetalation pathway most likely proceeds via the intermediate [(TRuPhos)(Ar)PdII(OTMS)], formed from the oxidative addition product and the base, which then reacts with the amine to yield the amido complex [(TRuPhos)(Ar)PdII(NR1R2)], although a direct metalation pathway between the oxidative addition product and the amide anion as strong base NaOtBu used, and a pathway through the adduct [(TRuPhos)(Ar)PdIIX(HNR1R2)] of the oxidative addition product to amine having less sterically hindered cyclic amines cannot be ruled out.

The exceptional efficiency of natural light-harvesting systems arises from their precisely organized supramolecular architectures. Reproducing such structural control in synthetic aqueous assemblies, particularly over size and dimensionality, remains a formidable challenge. Here, we report a general seeded-growth strategy that enables precise, hierarchical assembly of two-dimensional (2D) porphyrin heterostructures in water. Integrating pi-pi stacking, hydrogen bonding, and hydrophobic interactions, the porphyrin amphiphiles follow a metastable assembly pathway that yields kinetically controlled nanosheets or heterostructures. This approach provides unprecedented control over the nanostructure area across two orders of magnitude, establishing a versatile platform for complex functional architectures. By integrating a cobalt-porphyrin acceptor via block co-assembly, we construct 2D donor-acceptor heterostructures that achieve a directed energy funneling. Ultrafast spectroscopic analysis combined with global fitting reveals the mechanism: the controlled 2D heterostructures promote exciton migration at rates 2.5-fold greater than in homostructures and drive the formation of a fully charge-separated state on a sub-nanosecond timescale, with dynamics that scale with platelet dimensions. This work establishes a synthetic route to biomimetic 2D heterostructures and elucidates the structural determinants of directed exciton and charge flow, offering key design principles for advanced biomimetic systems.