An efficient synthesis of organothiophosphates from sodium sulfinates and chlorophosphines (R2PCl) is described. The mechanism involves a P(III) to P(V) rearrangement of S-O-PR2 species leading to S-P bond formation, which may be catalyzed by chloride ions generated in situ. Notably, the chlorophosphines play dual roles as both the phosphorus source and the reductant. The synthesis features mild conditions, short time, a broad substrate scope, and the use of a stable and odorless sulfur source.

The large-scale implementation of direct ethylene glycol fuel cells (DEGFCs) relies on the design of catalysts that possess exceptional activity, durability, and efficient C-C bond breaking ability. However, Pt and Pd-based nanomaterials continue to face challenges of low selectivity and slow reaction kinetics in driving the complete oxidation of ethylene glycol to CO2. In this work, a facile one-pot reduction method is reported for controllable synthesis of PtBi nanodendrites (PtBi-NDs) composed of ultrathin bimetallene subunits. In alkaline media, the composition optimized PtBi-NDs demonstrate outstanding activity and strong resistance to CO poisoning during the ethylene glycol oxidation reaction (EGOR). The PtBi-NDs show 5.8-fold higher mass activity, enhanced stability, and superior C1 selectivity relative to commercial Pt nanoparticles (Pt c-NCs). Most strikingly, PtBi-NDs deliver a higher power density (8.3 mW cm-2 ) than Pt c-NCs in DEGFCs. The theoretical analysis and experimental measurements explain that the introduction of Bi element into Pt induces d-p orbital hybridization and promotes electron transfer from Bi to Pt, thereby facilitating C-C bond cleavage and boosting EGOR kinetics. This work establishes an effective strategy for constructing Pt-based ultrathin bimetallenes and offers fundamental insights into boosting EGOR performance via d-p orbital hybridization.

Antibiotic contaminants accumulated in wastewater treatment plants are typically present at trace levels, making their removal challenging and thus necessitating the development of unique materials and technologies for efficient elimination. Here, we report a steam-assisted conversion method using water as the vapor source for the synthesis of four highly crystalline (3-ketoenamine-linked covalent organic frameworks (COFs). Among them, COF TpPa-SO3H, possessing a record-high BET surface area of 710 m2 g-1 and featuring ellipsoidal channels partitioned by multilayered sulfonate groups, exhibits strengthened shape-matched recognition and interactions (electrostatic and hydrogen bonding) toward typical antibiotics azithromycin (AZM) and ofloxacin (OFL), enabling their trace removal from water. The key to obtaining high crystallinity COFs via steam-assisted conversion lies in the competition between the reversible formation of a protonated amine salt intermediate phase and the reversible imine formation, which enhances the overall reversibility and error-correction of the COFs assembly. In the static adsorption experiment, COF TpPa-SO3H achieved removal efficiencies of up to 99.3% for both AZM and OFL (10-25 & micro;g L-1), and in breakthrough curves it can decrease AZM concentrations from 25 to 0.2 & micro;g L-1. This study provides valuable insights into the preparation of highly crystalline COFs and the deep removal of trace organic pollutants.

We report a palladium-catalyzed esterification reaction involving difluoroallyl bromides. This synthetic strategy involves the activation of fluorinated bromohydrocarbons by palladium catalysis and a direct C-O coupling reaction with a weakly nucleophilic indole carboxylic acid to obtain indole carboxylic esters. The key of this reaction lies in the selective coordination and activation of 3-bromo-3,3-difluoropropene by the palladium catalyst. The reaction overcomes the influence of the unique electronic effects of the difluoromethylene group on alkene reactivity, directly establishing an efficient new method for the synthesis of difluoroallyl esters, while exhibiting good substrate compatibility and moderate functional group tolerance. It not only applies to indole-based substrates but also can convert pyrrole/aromatic acids into the corresponding carboxylic esters. Overall, this study provides a practic al and straightforward synthetic approach for difluoroallyl-substituted indole/pyrrole/aromatic carboxylic esters.

Alkene difunctionalization via electrophilic aminyl radical cations offers a straightforward route to complex tertiary alkylamines widely occurring in biologically active molecules. However, only a limited variety of third reaction components have been hitherto introduced because of the challenges in capturing transient C(sp3)-centered radical intermediates under acidic conditions, and structurally specific alkenes are usually required. Herein, we report a copper-catalyzed three-component aminothiolation reaction, enabling the first incorporation of S-based functionalities across simple alkenes to synthesize β-thio tertiary alkylamines. This protocol works well for both aryl and unactivated alkenes with a broad functional group compatibility and is applicable to ─SCF3, ─SCN, and ─SBz groups. Mechanistic investigations reveal a key bimolecular homolytic (SH2) substitution process that efficiently traps the nascent C(sp3)-centered radical intermediates in acidic media and facilitates the C─S bond formation with high regioselectivity and even primary enantiocontrol. The introduced S-based functionality can improve the performance of pharmaceuticals such as Fentora.

We report a case of ruthenium-catalyzed esterification involving difluorobromoallyl. By coupling fluorinated halogenated hydrocarbons with phenolic compounds, difluoroallyl ethers are first formed, and then two molecules of hydrogen fluoride are removed under the action of a strong base to form acrylates. This chemical conversion process has the advantages of wide substrate applicability and strong functional-group tolerance. Finally, we also carried out derivatization reactions on some of the products formed by this chemical conversion, including the Heck reaction with halogenated hydrocarbons catalyzed by palladium, the addition reaction with liquid bromine, and the hydrogenation reduction reaction with hydrogen. It is worth mentioning that the acrylate directly left under the action of palladium on carbon. Phenolic products were formed. Finally, we also carried out the coupling reaction of phenyl acrylate and benzyl benzene. Single-crystal diffraction showed that the product was benzyl ether. These reactions all provide ideas and methods for the diversified transformation of acrylate compounds in the later stage.

Analytical pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) was used to investigate the catalytic fast pyrolysis of cellulose. The catalysts investigated in this study included rutile TiO2, anatase TiO2, Fe2O3, ZrO2, CeO2, CuO, CaO, and NiO. These catalysts exhibited distinct effects on the distribution of cellulose pyrolysis products. Among the tested catalysts, rutile TiO2 was the most effective in suppressing carbohydrate-derived products, reducing their relative content to 65.1

Isoprene is the most abundant biogenic volatile organic compound (BVOC) and has far-reaching impacts on secondary organic aerosol (SOA) formation globally. Its atmospheric oxidation produces diverse isomeric radicals that drive subsequent chain propagation and mechanistic branching. However, high-throughput experimental characterization of these isomeric-resolved radicals remains unavailable, leaving critical gaps in the underlying molecular mechanisms. Here we establish a radical-omics approach for isomer-specific identification and detection of hundreds of radical species generated during VOCs oxidation. Applied to OH-initiated isoprene oxidation, this method enables experimental quantification of four OH-added allylic radicals and determination of their branching ratios. We further found hydrogen-abstraction to be an unexpectedly important pathway, contributing up to 8.78 ± 3.96% of total branching. Incorporating the updated mechanism into a global chemical transport model shows that this pathway contributes up to 13.5% of isoprene-derived low-volatility SOA over tropical rainforests. These results provide an experimental foundation for radical screening and targeted mechanistic validation, revealing hidden pathways in complex atmospheric conditions.

We report an electrochemical strain-release driven cascade cyclization of N-aryl bicyclobutyl amides with 1,3-dicarbonyl compounds under mild conditions. This operationally simple electro-oxidative procedure enables sequential C(sp3)-H and C(sp2)-H functionalization, offering an efficient route to access functionalized spirocyclobutyl oxindoles in moderate to excellent yields, without the need for super-stoichiometric oxidants or noble-metal catalysts. In addition, the reaction demonstrates broad applicability across a wide range of symmetrical and asymmetrical 1,3-dicarbonyl compounds, including diesters, ketoesters and diketones.

A method for separating four main phenylethanoid glycosides (PhGs) from the extract of Cistanche tubulosa using Sephadex LH-20 gel chromatography combined with common filler octadecylsilane-bonded silica (ODS) gel column chromatography was established. The optimal preparation process parameters were determined through medium-pressure preparative chromatography using Cistanche tubulosa as the raw material. Four PhG monomers were successfully separated and purified. The optimal process parameters were as follows: a sample concentration of 100 mg/mL, a sample flow rate of 4 mL/min, a sample volume of 10 mL, an eluent with a volume fraction of 20

Dysregulation of intracellular Ca2+ signaling is a critical determinant of cell fate, however the contribution of non-canonical Ca2+ reservoirs to cancer-selective apoptosis remains incompletely understood. In this study, realgar transforming solution (RTS), a microbially processed arsenical, was employed as a biologically informative perturbation to investigate how lysosomal pH dysregulation a Ca2+-associated mitochondrial apoptotic program in triple-negative breast cancer (TNBC) cells. RTS exhibited superior selectivity compared with inorganic arsenic trioxide (ATO) and paclitaxel, significantly reducing the viability of TNBC cells (MDA-MB-231, BT-549, and MDA-MB-468) while sparing non-malignant MCF-10 A cells.. RTS-induced cell death was characterized by a Ca2+-dependent mitochondrial program—marked by cytochrome c release and caspase-9 activation—operating independently of reactive oxygen species accumulation and p53 signaling. Mechanistically, RTS triggered sustained cytosolic and mitochondrial Ca2+ overload originating from lysosomal mobilization rather than extracellular influx or endoplasmic reticulum depletion. Time-course profiling identified lysosomal acidic intensification as an early event, preceding TRPML1-mediated Ca2+ efflux and subsequent lysosomal membrane permeabilization (LMP). Consistently, pharmacological neutralization of the acidic shift (BafA1) or TRPML1 inhibition (ML-SI1) significantly attenuated the cytosolic Ca2+ elevation observed at the measured intervals. Collectively, these in vitro findings establish a “lysosome-mitochondria” signaling axis in which early pH perturbation represents a potential vulnerability in TNBC. While the multicomponent nature of RTS requires further characterization, this study provides preliminary insights into targeting organelle-specific Ca2+ hubs as a complementary strategy for refractory solid tumors.

Enantioselective cleavage of C−H and C−F bonds is a fundamental challenge in synthetic chemistry owing to their high bond dissociation energies. We now report a general cobalt/Salox catalytic platform that achieves this dual functionalization with α,α-difluoroallenes in high enantioselectivity and stereoselectivity. This versatile approach enables the diversity-oriented synthesis of enantiopure E-fluoroalkenyl N-heterocycles bearing phosphorus and carbon stereocenters, as well as C−N axial chirality, planar chirality, and inherent chirality. Combined experimental and computational mechanistic studies elucidate an unconventional CoIII/I/III/I catalytic cycle, which proceeds via a sequential cascade of C(sp2)−H metalation, allene insertion, reductive elimination, C(sp3)−H oxidative addition, alkene isomerization, and β-F elimination.

A visible light-mediated divergent synthesis of 2,3-dihydrobenzofuran selenides via cascade cyclization/selenylation of 2-allyloxyaryl sulfonium salts with diselenides is reported. The protocol offers a safer alternative to toxic PhSeCl for constructing biologically selenylated heterocycles in moderate to excellent yields. This method exhibits broad substrate scope, good functional group tolerance, and practical scalability. Mechanistic studies support a radical cascade pathway involving 5-exo-trig cyclization.

Lignin represents the largest renewable source of aromatic building blocks in nature, underscoring the need for simple and efficient methodologies to convert it into high-value aromatic chemicals. In this context, the selective oxidation of lignin and its derivatives to aryl carboxylic acids under mild conditions is of great significance. Herein, we report a simple yet recyclable VOCl3 catalyst for visible-light-induced selective aerobic oxidation that enables the direct conversion of raw biomass feedstocks (e.g., wheat straw, rice straw, and corn straw), which serve as abundant and renewable sources of lignin, into aryl carboxylic acids using ambient air as the oxidant. Furthermore, the resulting carboxylic acids are readily applicable to a developed organic charge-transfer-complex-induced chemoselective decarboxylative functionalization. Mechanistic investigations employing a beta-O-4 linkage in lignin model compounds reveal that VOCl3 plays a dual role in both a ligand-to-metal charge transfer (LMCT) process and a chlorine-radical-induced hydrogen atom transfer (HAT) process. Specifically, the VOCl3-catalyzed LMCT process generates a C-alpha-O-centered radical to induce the cleavage of the C-alpha-C-beta bond to afford the corresponding aryl aldehyde, which is subsequently oxidized to the aryl carboxylic acid via a HAT process driven by the chlorine radical-generated in situ from VOCl3. Notably, despite the structural simplicity of VOCl3, it exhibits decent recyclability, maintaining 81% of its initial activity after nine consecutive runs, outperforming conventional well-defined molecular catalysts, which typically suffer from deactivation under aerobic oxidative conditions. This work offers insights into the design of simple yet robust catalytic systems for the upgrading of raw biomass into valuable aromatic chemicals.

Dysregulation of intracellular Ca2+ signaling is a critical determinant of cell fate; however the contribution of non-canonical Ca2+ reservoirs to cancer-selective apoptosis remains incompletely understood. In this study, realgar transforming solution (RTS), a microbially processed arsenical, was employed as a biologically informative perturbation to investigate the potential link between lysosomal pH dysregulation and a Ca2+-associated mitochondrial apoptotic program in triple-negative breast cancer (TNBC) cells. RTS displayed selective inhibitory activity compared with inorganic arsenic trioxide (ATO) and paclitaxel, leading to reduced viability of TNBC cells (MDA-MB-231, BT-549, and MDA-MB-468) while showing minimal impact on non-malignant MCF-10 A cells. RTS-induced cell death was linked to a Ca2+-mediated mitochondrial program-marked by cytochrome c release and caspase-9 activation-while showing limited correlation with reactive oxygen species (ROS) accumulation or p53 signaling. Mechanistically, RTS triggered sustained cytosolic and mitochondrial Ca2+ overload derived primarily from lysosomal mobilization rather than extracellular influx or endoplasmic reticulum depletion. Time-course profiling observed lysosomal acidic intensification as an early event, preceding TRPML1-mediated Ca2+ efflux and subsequent lysosomal membrane permeabilization (LMP). Consistently, pharmacological neutralization of the acidic shift (BafA1) or TRPML1 inhibition (ML-SI1) significantly attenuated the cytosolic Ca2+ elevation observed at the measured intervals. Collectively, these in vitro findings highlight a potential"lysosome-mitochondria" signaling axis in which early pH perturbation may represent a vulnerability in TNBC. While the multicomponent nature of RTS requires further characterization, this study provides preliminary insights into targeting organelle-specific Ca2+ hubs as a possible complementary strategy for refractory solid tumors.

Merging photochemistry with transition-metal-catalyzed asymmetric C-H functionalization represents a highly attractive yet underexplored strategy for the sustainable synthesis of valuable enantiopure molecules. Herein, we report a synergistic catalytic system that combines visible light photoredox catalysis with cobalt catalysis to achieve enantioselective C-H/N-H annulation under mild conditions. The protocol accommodates nine types of alkynes, including internal, terminal, and functionalized derivatives, as well as terminal allenes, providing unified access to carbon- and phosphine-stereogenic N-heterocycles with broad functional group tolerance, high yields, and excellent enantioselectivity.

A new FeSO4-catalyzed cascade nitration/cyclization and 6-exo-trig dearomatization reaction of biaryl ynones was developed. A variety of nitrated spiro[5.5]trienones were prepared in good yields using cheap and readily available Co(NO3)2.6H2O as nitration reagent.

The efficient assembly of nitrogen- and sulfur-containing heterocycles remains a central objective in modern synthetic chemistry. Herein, we report a visible-light-mediated [3+2] cycloaddition between arylidenecyclopropanes and N-sulfinylamines, utilizing commercially available trimethylsilyl azide (TMSN3) as a radical mediator. This transformation employs 4CzIPN as an organophotocatalyst at room temperature under metal- and oxidant-free conditions, providing a concise and atom-economical procedure for diverse five-membered cyclic sulfinamides in moderate to good yields with high selectivity, a broad substrate scope, and excellent functional group tolerance. Density functional theory (DFT) calculations revealed that the transformation proceeds via a sequential mechanism involving radical initiation, addition, ring opening, cyclization, and elimination.

Abstract: Aryl imidazole trifluoromethylation is an important class of organic compounds with significant application prospects in fields such as biomedicine, pesticides, and optoelectronic materials. This paper investigates the efficient synthesis of a series of trifluoromethylated phenyl imidazole organic molecules by reacting cheaply and readily available 2-bromotrifluoropropene directly with imidazole compounds such as phenyl imidazole/benzyl imidazole through base catalysis. The molecular structures of the products were determined by means such as single crystal cultivation, and common parameters of the crystals were studied to ascertain their structures. Additionally, the biological bactericidal activity of some compounds was investigated, and preliminary results indicated that some molecules exhibited significant bactericidal effects against escherichia coli and staphylococcus aureus. Finally, theoretical calculations using DEPT were conducted to study the possible transition states involved in the reaction and the chemical selectivity of the products. This provides a solid foundation for future research on this type of aryl imidazole trifluoromethylation.