Dynamic Covalent Sulfur-Selenium Rich Polymers via Inverse Vulcanization for High Refractive Index, High Transmittance, and UV Shielding Materials.

Recent advancements in inverse vulcanization have led to the development of sulfur-rich polymers with diverse applications. However, progress is constrained by the harsh high-temperature reaction conditions, limited applicability, and the generation of hazardous HS gas. This study presents an induced IV method utilizing selenium octanoic acid, yielding sulfur-selenium rich polymers with full atom economy, even at a low-temperatures of 100-120 °C.

Synthesis of 1,4,2-Diazaphospholidine-3,5-diones Using Na(OCP) as the "P" Source.

A refined synthesis of 1,4,2-diazaphospholidine-3,5-dione derivatives was achieved through a cyclization reaction involving Na(OCP) and isocyanates. Na(OCP) was demonstrated to be a relatively stable and safe source of phosphorus, enabling the production of diverse 1,4,2-diazaphospholidine-3,5-dione derivatives with high yields. The reaction proceeds efficiently under catalyst-free and mild conditions.

Potassium Phosphate-Mediated Synthesis of C4-Phosphorylated Quinolines via Cascade Cycloisomerization of Ynones.

A cascade phosphorylation cycloisomerization of readily accessible ynones and diphenylphosphine oxides facilitated by potassium phosphate is described, allowing for the straightforward synthesis of C4-phosphorylated quinoline scaffolds. The formation of a C-P bond and a C-N bond is achieved in a single procedure without the need for pre-assembled quinoline cores prior to phosphorylation. This transformation operates without the requirement for metals or oxidants and exhibits excellent compatibility with various functional groups.

Formation of atmospheric molecular clusters containing nitric acid with ammonia, methylamine, and dimethylamine.

This study investigates the formation of atmospheric molecular clusters containing ammonia (NH, A), methylamine (CHNH, MA), or dimethylamine (CHNHCH, DMA) with nitric acid (HNO, NA) using quantum mechanics. The Atmospheric Cluster Dynamic Code (ACDC) was employed to simulate the total evaporation rate, formation rate, and growth pathways of three types of clusters under dry and hydrated conditions. This study evaluates the enhancing potential of A/MA/DMA for NA-based new particle formation (NPF) at parts per trillion (ppt) levels.

Selective Synthesis of Mono- and Bis-Phosphorylated (Dihydro)pyrans via TMSCl-Mediated Cascade Phosphorylation Cycloisomerization of Enynones.

A chlorotrimethylsilane (TMSCl)-mediated cascade phosphorylation and cycloisomerization of enynones with diphenylphosphine oxides is presented. This methodology enables the highly selective synthesis of monophosphorylated 2-pyrans and bisphosphorylated dihydropyrans through precise solvent-reagent stoichiometry control. The strategy demonstrated excellent functional group compatibility and high yields (up to 96%), providing facile access to structurally diverse phosphorylated heterocycles with potential applications in medicinal chemistry and materials science.

Palladium-Catalyzed Four-Component Radical Cascade Carbonylation Access to 2,3-Disubstituted Benzofuran Derivatives.

Multicomponent radical tandem reactions have emerged as a crucial technique for synthesizing complex molecules in organic chemistry. In this study, we report a palladium-catalyzed four-component difluoroalkylative carbonylation of enynes and ethyl difluoroiodoacetate. This transformation proceeds through a multistep sequential reaction that introduces reactive difluoro and carbonyl groups while constructing the benzofuran skeleton.

A switch strategy for the synthesis of C4-ethylamine indole and C7-aminoindoline controllable carbon elimination.

Controllable β-carbon elimination to extrude norbornene remains a long-standing challenge in palladium and norbornene chemistry. Herein, this manuscript describes a switchable synthesis of biologically active C4-ethylaminoindole and C7-aminoindoline scaffolds by controlling β-carbon elimination, utilizing aziridine as a C-H ethylamination reagent through a C-N bond cleavage reaction. Furthermore, the protecting groups of the product can be easily removed, offering an unusual method for the synthesis of dopamine receptor agonists.

Nickel-Catalyzed Narasaka-Heck Cyclization Carbonylation of Unsaturated Oxime Esters with Arylboronic Acids.

The Narasaka-Heck reaction is one of the most straightforward methods for constructing pyrroline derivatives. Herein, we report a novel nickel-catalyzed three-component carbonylation reaction, which cleverly realizes the continuous construction of C(sp)-N bonds and C(sp)-C(sp) bonds and effectively promotes the synthesis of acyl-substituted pyrroline derivatives. Furthermore, this strategy not only expands the conversion pathway of γ,δ-unsaturated oxime esters but also provides a new method for the synthesis of nitrogen-containing heterocyclic compounds.

Synthesis of 1,2,4-diazaphospholes base-promoted cyclization reaction of hydrazonoyl chlorides and [BuN][P(SiCl)].

Aromatic 1,2,4-diazaphospholes featuring distinct hybrid-mode nitrogen atoms (N(λσ), N(λσ)) and low-valent phosphorus atoms (λσ) exhibited the characteristic of serving as unique hybrid ligands. This study presented a one-pot reaction involving the base-promoted stepwise cyclization of hydrazonoyl chlorides and [BuN][P(SiCl)] to yield 1,2,4-diazaphospholes, providing an effective method for synthesizing such compounds.

Fluoride-Mediated Aryne 1,2-Difunctionalization Involving C═S Bond Heterolysis.

We have successfully synthesized a series of bidentate ligands by utilizing 2-(trimethylsilyl)phenyl trifluorosulfonate as a precursor for the benzyl group. This method proceeded by inserting a polythiourea into the C═S π-bond, intramolecular ring proton migration, and ring opening. Salient features of this strategy are mild reaction conditions, a novel product structure, excellent stereochemistry, and a good functional group tolerance.

Direct Synthesis of C4-Acyl Indoles via C-H Acylation.

The direct synthesis of C4-acyl indoles deprived of C2 and C3 substituents has proven to be challenging, with scarce efficient synthetic routes being reported. Herein, we disclose a highly site-selective palladium-catalyzed C-H acylation for the construction of C4-acyl indoles via a Catellani-Lautens cyclization strategy. In addition, we systematically studied the C-H acylation mechanism of iodoaniline through density functional theory (DFT) calculations and combined experimental results to elucidate the principle of high chemoselectivity brought by triazine benzoate as an acylation reagent.

Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives.

A novel three-component cyclization carbonylation reaction of iodoarene-tethered propargyl ethers with amine and CO is reported. This palladium-catalyzed cascade reaction undergoes a sequence of oxidative addition, unsaturated bond migration, carbonyl insertion, and nucleophilic attack to deliver the benzofuran skeleton. Both aromatic amines and aliphatic amines could proceed smoothly in this transformation under one atm of CO.

Interaction between hydroxymethanesulfonic acid and several organic compounds and its atmospheric significance.

The interactions of the micro-mechanism of hydroxymethanesulfonic acid (HMSA) with the typical small organic molecule in atmospheric (X = methanol, formaldehyde, formic acid, methyl formate, dimethyl ether, acetone) has been investigated by density functional theory (DFT), quantum theory of atoms in molecules (QTAIM), Generalized Kohn-Sham Enery Decomposition Analysis (GKS-EDA) and the atmospheric clusters dynamic code (ACDC). The results of DFT show that the stable six- to eight-membered ring structures are easily formed in HMSA-X clusters. According to the topological analysis results of the AIM theory and the IRI method, a strong hydrogen bonding interaction is present in the complex.

Hydrazone Phosphaketene as a Synthetic Platform To Obtain Three Classes of 1,2,4-Diazaphosphol Derivatives by Switchable Chemoselectivity Strategies.

We introduce switchable chemoselectivity strategies based on the hydrazone phosphaketene intermediate to synthesize three classes of 1,2,4-diazaphosphol derivatives. First, the five-membered heterocyclic P and O anion intermediates acted as nucleophilic agents in the selective construction of C-P and C-O bonds. Second, the phosphinidene served as a phosphorus synthon, allowing for the formation of C-P and C-N bonds.

Template Synthesis to Solve the Unreachable C-H Functionalization Reaction of Aryl Iodide.

This report describes the use of a simple Pd/NBE catalytic system to achieve C-H oxylation and phosphonylation and other functionalizations of aryl iodide through templated conversion reactions. Dimethylamine is introduced in the -site of aryl iodide through C-H amination, and aryl dimethylamine is quickly converted to methyl quaternary ammonium salt precipitation. Methyl quaternary ammonium salt avoids Hofmann elimination in subsequent functionalization.

Synthesis of 3(2)-furanone derivatives: -TsOH/halotrimethylsilane promoted cycloketonization of -hydroxyl ynones.

A -TsOH/halotrimethylsilane facilitated cycloketonization of -hydroxyl ynones is detailed. This methodology enables the one-step synthesis of polysubstituted 3(2)-furanone products. It is remarkable that the reaction exhibits excellent regio- and chemoselectivity by the addition of very small quantities of -toluenesulfonic acid and water.

Regioselective C-H Active Carbonylation via 1,4-Palladium Migration.

We report a highly regioselective three-component coupling reaction of styrene, CO gas, and an amine compound to synthesize multisubstituted α,β-unsaturated amides, which involves a palladium-catalyzed sequential 1,4-palladium migration, C(sp)-H activation, carbonylation, and amination. Salient features of this strategy include the use of 1 atm of CO, excellent stereochemistry, and good functional group tolerance. Further, a series of control experiments and density functional theory calculations were performed to afford some insights for the transfer mechanism.

Redox Neutral Radical-Relay Nickel-Catalyzed Remote Carbonylation.

A novel and efficient method for the catalytic installation of a carbonyl group via remote radical coupling is disclosed. The nickel-catalyzed reaction proceeds to undergo a sequential single-electron transfer, 1,5-hydrogen atom transfer, and carbonyl insertion, thus providing the α-substituted ketone. Further, this reaction could be carried out smoothly under normal pressure and redox-neutral conditions, and demonstrated functional-group compatibility and excellent site-selectivity.

Direct synthesis of phosphorotrithioates from [TBA][P(SiCl)] and disulfides.

Sulfur-containing organophosphorus molecules have played a pivotal role in organic synthesis, pharmaceutical pesticides and functional materials, thereby motivating researchers worldwide to establish S-P bonds from more environmentally friendly phosphorus sources. In this study, a novel method was developed for constructing S-P bonds, specifically by reacting the inorganic phosphorus derivative TBA[P(SiCl)] with sulfur-containing compounds under mild conditions. This method demonstrates the advantages of low energy consumption, mild reaction conditions and environmental friendliness.

Synthesis of C4-Aminated Carbazoles and Their Derivatives via Pd/NBE Chemistry.

Carbazole, as one of the most important organic frameworks, has been used in optoelectronic materials and biochemistry. However, the synthesis of C4-substituted carbazole has always been an unsolved problem. This report describes the one-step synthesis of C4-aminated carbazoles and their derivatives through the series reaction of C-H amination and arylation.

Nickel-Catalyzed Three-Component Tandem Radical Cyclization 1,5-Difunctionalization of 1,3-Enynes and Alkyl Bromide.

A nickel-catalyzed three-component tandem radical cyclization reaction of aryl bromides with 1,3-enynes and aryl boric acids to construct γ-lactam-substituted allene derivatives has been described. This protocol provides lactam alkyl radicals through the free radical cyclization process, which can be effectively used to participate in the subsequent multicomponent coupling reaction so that 1,3-enynes could directly convert into corresponding poly-substituted allene compounds. In addition, this efficient method enjoys a broad substrate scope and provides a series of 1,5-difunctionalized allenes in a one-pot reaction.

Access to Polysubstituted Halophosphorylated Dihydrofurans via Halotrimethylsilane-Promoted Cascade Cyclization of γ-Hydroxyl Ynones with Diphenylphosphine Oxides.

A halotrimethylsilane (TMSX) accelerated cascade halophosphorylation and cycloisomerization of γ-hydroxyl ynones with diphenylphosphine oxides is presented. This methodology allows the one-step synthesis of practical polysubstituted halophosphorylated dihydrofuran derivatives. It is noteworthy that halotrimethylsilane functions as a halogenation reagent as well as a promoter to initiate this transformation.

Photoinduced inverse vulcanization.

The inverse vulcanization (IV) of elemental sulfur to generate sulfur-rich functional polymers has attracted much recent attention. However, the harsh reaction conditions required, even with metal catalysts, constrains the range of feasible crosslinkers. We report here a photoinduced IV that enables reaction at ambient temperatures, greatly broadening the scope for both substrates and products.