The development of operationally simple and environmentally benign synthetic strategies for constructing phosphorus-substituted heterocycles is highly valuable in organophosphorus chemistry. Herein, we report a straightforward and green radical cascade cyclization of diphenylphosphine oxide with isocyanides or heteroarenes for the synthesis of phosphorylated heteroarenes with high atom economy. With air as a green oxidant and ethanol as the solvent, without additional oxidants or bases, this one-pot protocol exemplifies the principles of green chemistry, enabling the construction of C-P and C-C bonds using an inexpensive, commercially available and low-toxicity catalyst. Studies on electron paramagnetic resonance and control experiments indicated that manganese(III) salt and O2 act in concert to achieve radical cascade cyclization, with superoxide radical anion (O2•-) contributing to this reaction.

A metal-free photocatalytic method achieves the selective radical cyclization of 1,5-enynes to construct naphthalene skeletons. This method utilizes an in situ-formed electron donor-acceptor (EDA) complex between sulfonyl chlorides and catalytic TBAI, delivering 4-cyano-1-sulfonyl naphthalenes through a 6-endo cyclization or a 5-exo-trig addition/3-exo-trig cyclization/ring expansion sequence. This one-pot transformation exhibits broad substrate scope and excellent functional group tolerance, efficiently forging both C-S and C-C bonds.

The present study evaluates the production of new neutron-rich isotopes in the rare-earth region ( Z= 61-71 ) using projectile fragmentation of primary beams at 800 MeV/nucleon at the HIgh-rigidity Radioactive Ion Beam Line (HIRIBL) of the High-Intensity heavy-ion Accelerator Facility (HIAF). The production potential of various projectiles was evaluated through measured and calculated production cross sections, revealing that ^198 Pt may offer a clear advantage for accessing this region. With an optimized target thickness, fragmentation of ^198 Pt could lead to the discovery of about 30 new isotopes in the rare-earth region at HIAF, thereby providing a strong opportunity for studies in both nuclear physics and nuclear astrophysics at HIAF.

Herein, we report a silver-mediated cascade cyclization of 1,5-enynes with diazo compounds for the direct synthesis of pyrazolo[5,1-a]isoindoles from simple acyclic precursors. This one-pot process forges two rings and three new bonds via a sequential [3+2] cycloaddition/elimination/intramolecular aza-addition. The protocol features mild conditions, a broad substrate scope, and good functional group tolerance, and the products can be readily transformed into diverse valuable derivatives.

The efficient chemical recycling of polyethylene terephthalate (PET) remains a key challenge for sustainable polymer management. Herein, we report a series of tunable titanate nanostructured catalysts prepared via NaOH-controlled hydrothermal synthesis of TiO2, which enables systematic tuning of catalyst morphology and surface area. Among them, the optimized TN-10 catalyst exhibits an interconnected nanotubular architecture with a high specific surface area ( 184 m2 g-1). TN-10 efficiently catalyzes PET methanolysis under moderate reaction conditions, delivering 84

A series of potentially bioactive indolones were synthesized under light irradiation via catalyst-free electron do-nor-acceptor(EDA)complexes formed between arylthionium salts and unsaturated arylamide compounds.The photoexcited EDA complex generated an aryl radical,which subsequently underwent radical addition followed by intramolecular cyclization to yield the desired products.The reaction exhibited high regioselectivity.Additionally,based on preliminary studies of the reaction mechanism,a plausible catalytic cycle for the tandem radical reaction has been proposed.

A catalyst-free carbopyridylation reaction of maleimides with N-benzoylmethylpyridinium bromides under visible light irradiation is reported. The carbo-2-pyridylation products of maleimides are obtained in good yields, demonstrating broad substrate scope and high functional group tolerance even on a gram scale. Mechanistic studies suggest that the process involves a tandem [3+2] cycloaddition, and Norrish-type-II fragmentation.

A visible‐light‐promoted C−H amidation of (hetero)arenes with hypervalent iodine reagents has been successfully achieved with good yields. The high efficiency, broad substrate range and good functional group compatibility demonstrated the utility of the method. Moreover, this protocol was suitable for the late‐stage functionalization of natural products. Mechanistic studies have shown that the N‐centred saccharin radical mediates C−H amidation of arenes.

The development of operationally simple and efficient synthetic methodologies for constructing heteroarylamines is highly valuable in modern synthetic chemistry. Herein, we describe a visible-light-induced, mild, oxidant- and reductant-free radical-radical coupling between pyridylphosphonium salts and arylamines for their synthesis. This protocol exhibits excellent regioselectivity, broad substrate scope, and good functional group tolerance, enabling the late-stage functionalization of complex drug molecules and providing a sustainable pathway to valuable aromatic amines. Mechanistic studies indicate that DABCO acts as a key mediator, facilitating two sequential single-electron transfer (SET) and deprotonation processes.

Herein, ruthenium(II)‐catalyzed CH activation/annulation of α‐carbonyl phosphoniums with CF3‐imidoyl sulfoxonium ylides is carried out to generate a series of 3‐trifluoromethyl‐isoquinolones in 44–98% yields. A plausible mechanism involving a cascade CH activation of arenes, formation of ruthenium(II) carbenoid, migratory insertion of the Ru−aryl bond, and intramolecular aza‐cyclization is proposed. In addition, the reaction procedure features simple synthesis, wide substrate scope, and excellent functional group compatibility. Furthermore, the application potential of the developed protocol is demonstrated through successful scale‐up experiments and subsequent transformations.

Nuclear transmutation is emerging as a promising approach for reprocessing high-level waste, specifically treating long-lived nuclides like Zr-93 from spent fuel. It is essential to accumulate reaction data for these nuclei to advance this prominent treatment and to build a comprehensive understanding of reaction mechanisms. In this study, the residual production cross-sections resulting from proton-induced reactions on Zr-93 were measured at 27 MeV/nucleon in inverse kinematics. At the RI Beam Factory (RIBF), the Optimized Energy Degrading Optics beamline was used to deduce production cross-sections for isotopes Nb91-93, Zr-91,Zr-92, and Y-88,Y-89. Comparing the results from this study and prior research with calculated excitation functions, a moderate agreement is found with theoretical predictions derived from TALYS and CCONE. The measured cross-sections offer valuable insights for future considerations in nuclear-waste treatment facilities. This is particularly relevant for facilities exploring innovative methods, such as accelerator-driven systems.

Herein, visible‐light‐induced metal‐free three‐component amidoheteroarylation of alkenes with quinoxalin‐2(1H)‐ones and N‐sulfonylaminopyridinium salts is developed. This protocol involves a radical relay process in which the N‐centered radicals undergo chemoselective addition to alkenes to form an alkyl radical that selectively combines with heteroarenes, leading to the formation of C−C and C−N bonds in one step under mild reaction conditions. The involved high efficiency and selectivity, wide substrate scope, and excellent functional‐group compatibility demonstrate the practicability of the developed protocol.

The increasing use of fluorine-containing bioactive molecules necessitates efficient strategies for fluorinated group installation. Despite the impressive development of photoinduced radical fluoroalkylation as a powerful tool for introducing fluorine, the persistent issues, including the recyclability and reaction specificity of homogeneous photocatalysts, still leave great room for further advancement in a sustainable and general fashion. Herein, we report a conceptually different approach toward multiple types of fluoroalkylations by using recoverable and versatile graphitic carbon nitride (g-CN) nanosheets as a heterogeneous photocatalyst. This photocatalytic system enables diverse intermolecular fluoroalkylations of alkenes with fluoroalkanesulfinates and intramolecular fluoroalkyl migrations of alkenyl triflates. Detailed characterizations and mechanism studies substantiate the stability of this organic semiconductor and the crucial role of photogenerated electron-hole pairs. In this article, we describe a stable semiconductor material, g-CN nanosheets, can serve as a heterogeneous photocatalyst to accomplish intermolecular fluoroalkylation of assorted alkenes with fluoroalkanesulfinates and intramolecular fluoroalkyl migration of alkenyl triflates. The inexpensive and easy-prepared g-CN nanosheets can be recycled for several runs with conserved activity.+ image

Incorporating metal clusters into the confined cavities of metal-organic frameworks (MOFs) to form MOF-supported catalysts has attracted considerable research interest with regard to carbonylation reactions. Herein, a self-templating method is used to prepare the zinc oxide (ZnO)-supported core-shell catalyst ZnO@Pd/ZIF-8. This facile strategy controls the growth of metal sources on the ZIF-8 shell layer and avoids the metal diffusion or aggregation problems of the conventional synthesis method. The characteristics of the catalysts show that the palladium (Pd) clusters are highly dispersed with an average particle size of approximate to 1.2 nm, making them excellent candidates as a catalyst for carbonylation under mild conditions. The optimal catalyst (1.25-ZnO@Pd/ZIF-8) exhibits excellent activity in synthesizing alpha, beta-alkynyl ketones under 1 atm of carbon monooxide (CO), and the conversion rate of 1, 3-diphenylprop-2-yn-1-one is 3.09 and 3.87 times more than those of Pd/ZIF-8 and Pd2+, respectively, for the first 2 h. Moreover, the 1.25-ZnO@Pd/ZIF-8 is recyclable, showing negligible metal leaching, and, under the conditions used in this investigation, can be reused at least five times without considerable loss in its catalytic efficiency. This protocol can also be applied with other nucleophile reagents to synthesize esters, amides, and acid products. The zinc oxide (ZnO)-supported core-shell catalyst ZnO@MOF, with small apertures on the catalyst surface, provides a potential advantage for isolating metal-atom or metal-clusters sources as guests, which has a positive effect on the stability and activity of the catalyst. These results demonstrate the benefit of using core-shell ZnO@ZIF-8 as a platform for immobilizing ultrasmall Pd clusters for multiple carbonylation reactions.image

A visible‐light‐promoted radical fluoroalkylation has been achieved through a three‐component reaction of fluoroalkyl reagents, isocyanides and water, affording fluoroalkyl‐substituted amides in good yields. This reaction involves the generation of the nitrilium cation by single‐electron reduction of the imidoyl radical and a subsequent nucleophilic attack by water. Mechanistic studies support the generation of the imidoyl radical through the capture of the fluoroalkyl‐substituted imidoyl radical species.

The deuteron is a loosely bound system that can easily break up into its constituent proton and neutron whilst in the presence of Coulomb and nuclear fields. Previous experimental studies have shown that this breakup process has a significant impact on residual-nucleus production from deuteron bombardment in the high-energy range of 50-210 MeV/nucleon. However, there remains a lack of cross-section data at energies below 50 MeV/nucleon. The current study determined Zr-93 + d reaction cross sections under inverse kinematics at approximately 28 MeV/nucleon using the BigRIPS separator, OEDO beamline, and SHARAQ spectrometer. Cross sections from this research were compared with previous measurements and theoretical calculations. The experimental results show a large enhancement of the production cross sections of residual nuclei, especially those produced from a small number of particle emissions, compared to the proton-induced reaction data at similar bombarding energy. The DEURACS calculation, which quantitatively takes deuteron-breakup effects into account, reproduces the data well. As a long-lived fission product, Zr-93 remains a challenge for nuclear-waste disposal and treatment. This study's low-energy data may assist future consideration of nuclear-waste treatment facilities, where Zr-93 + d may feasibly transmute the waste into short-lived/stable nuclei.

In this study,a visible-light photoredox-catalyzed difluoroalkylation of newly designed functionalized aromatic isocyanides with commercially available CF2 precursors was reported.A series of CF2-containing indole-1,2-fused diaze-panones were constructed in cascade reaction through a sequence of radical addition/cyclization processes under mild condi-tions.This reaction not only generated a class of polycyclic indole fused seven-membered nitrogen heterocycles but also ex-panded the reactions of functionalized isocyanides.

有机硫化物广泛存在于石油、煤炭等自然资源中,具有丰富的资源储备.在石油炼制工业中,通常需要通过C-S断裂进行石油馏分的脱硫.其中,过渡金属催化的C-S断裂反应因具有效率高、条件温和、污染小等优点而备受研究者的关注.总结了过渡金属催化不同类型有机硫化物C-S断裂反应的最新进展,对Pd、Cu、Ni、Fe等催化体系的反应机理提出了见解,并对该类反应的发展前景进行了展望.

The cleavage and functionalization of C-S bonds have become a rapidly growing field for the design or discovery of new transformations. However, it is usually difficult to achieve in a direct and selective fashion due to the intrinsic inertness and catalyst-poisonous character. Herein, for the first time, we report a novel and efficient protocol that enables direct oxidative cleavage and cyanation of organosulfur compounds by heterogeneous nonprecious-metal Co-N-C catalyst comprising graphene encapsulated Co nanoparticles and Co-Nx sites using oxygen as environmentally benign oxidant and ammonia as nitrogen source. A wide variety of thiols, sulfides, sulfoxides, sulfones, sulfonamides, and sulfonyl chlorides are viable in this reaction, enabling access to diverse nitriles under cyanide-free conditions. Moreover, modifying the reaction conditions also allows for the cleavage and amidation of organosulfur compounds to deliver amides. This protocol features excellent functional group tolerance, facile scalability, cost-effective and recyclable catalyst, and broad substrate scope. Characterization and mechanistic studies reveal that the remarkable effectiveness of the synergistic catalysis of Co nanoparticles and Co-Nx sites is crucial for achieving outstanding catalytic performance.

A ruthenium(II)-catalyzed hydroamination of allenoates with arylamines has been developed. This strategy provides an approach to synthesize E-allylic amines in good yields with high atom-economy and high levels of chemo-, regio- and E-selectivities with a broad substrate scope.