Chemistry - A European Journal最新文献

{"title":"Stereoselective Syntheses of Cyclic Microsclerodermin Derivatives.","authors":"Kevin Bauer, Uli Kazmaier","doi":"10.1002/chem.202502459","DOIUrl":"https://doi.org/10.1002/chem.202502459","url":null,"abstract":"<p><p>Starting from l-xylose and d-arabinose, six different cyclic microscleroderma derivatives were successfully obtained. Key steps of the syntheses are, on the one hand, Sakurai allylations, whose stereochemical course depends on the Lewis acid used, and on the other hand, photochemical Wolff rearrangements in the presence of complex aminofuranosides. Finally, aromatic side chains were introduced via cross metathesis.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02459"},"PeriodicalIF":3.7,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The N-Bromo-Hammick Intermediate.","authors":"Virinder Bhagat, J Philipp Wagner","doi":"10.1002/chem.202502434","DOIUrl":"https://doi.org/10.1002/chem.202502434","url":null,"abstract":"<p><p>We report the characterization of bromopyridin-2-ylidene, the N-bromo-Hammick intermediate, isolated in solid neon at 4.4 K. Computations (B2PLYP, NEVPT2), IR, and UV/vis spectroscopy characterize this intermediate as a singlet carbene with a vacant σ*-type frontier orbital. This unusual electronic structure (σ²σ*⁰) allows the carbene to isomerize to its more stable pyridine tautomer via a planar transition state, avoiding the deviation from planarity seen in other singlet carbenes. The compound's reaction with molecular hydrogen faces a minor but prohibitive barrier (8.4 kcal mol^-1) at the low temperatures of the experiment.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02434"},"PeriodicalIF":3.7,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of Cyclobutane-Containing Tricyclic β-Lactams Based on a Saturated Scaffold Enabled by Iron-catalysed [2 + 2]-Cycloaddition.","authors":"Lea Freitag, Johannes Zeh, Levi A Ziegenhagen, Felix J Becker, Dragoș-Adrian Roșca","doi":"10.1002/chem.202502476","DOIUrl":"https://doi.org/10.1002/chem.202502476","url":null,"abstract":"<p><p>Highly saturated, three-dimensional β-lactams are valuable motifs in medicinal chemistry, yet general routes to cyclobutane-fused analogues remain scarce. Here we disclose a concise strategy that delivers pyrrolidine-, piperidine-, and azepane-based tricyclic β-lactams. A pyrimidinediimine-iron catalyst first constructs the cyclobutane ring and the N-heterocycle in one step through an intermolecular [2 + 2]-cycloaddition of allyl amines; a subsequent photochemical intramolecular C─H insertion then forges the β-lactam. The major products adopt rigid, cage-like conformations confirmed for the pyrrolidine series by single-crystal X-ray diffraction. Comprehensive conformer sampling (using CREST), DFT-calculated NMR shifts, and DP4 statistical analysis establish the stereochemistry across the library. Strain-release opening of the β-lactam ring furnishes methylphenidate analogues in a single step, underscoring the scaffolds' synthetic versatility. Comparative studies on the corresponding bicyclic systems highlight the unique three-dimensionality imparted by the additional cyclobutane ring, further expanding the toolbox for lead-oriented synthesis.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02476"},"PeriodicalIF":3.7,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145172079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"κ²-N,N'-Sulfurdiimide and κ¹-O-Sulfinylamine Complexes of Tin(IV) Chloride.","authors":"Nathan D D Hill, René T Boeré","doi":"10.1002/chem.202502342","DOIUrl":"https://doi.org/10.1002/chem.202502342","url":null,"abstract":"<p><p>A series of Sn(IV) chloride complexes with sulfur diimide (SDI, R-NSN-R) ligands are presented, including structural characterization of first-in-class complexes of bidentate diaryl-SDIs, [SnCl₄{κ²-N,N'-S(NAr)₂}] (Ar = 4-X-C₆H₄-), and an oxygen-coordinated sulfinylamine, [SnCl₄{κ¹-O-OSNPh}₂]. As part of the comprehensive experimental and DFT computational investigation, ¹¹⁹Sn NMR analysis revealed a dynamic exchange equilibrium in acetonitrile between SDI ligands and solvent, providing insight into their complicated solution-state chemical and electrochemical behavior. Voltammetric experiments show that, despite this dynamic equilibrium, the SDI ligands appear to suppress typical Sn(IV) reduction pathways. While tentative due to the complex behavior, this suggests that SDIs are functioning as redox-active (RA) ligands. In conjunction with our previous systematic characterization of diaryl-SDIs, these findings highlight their potential as an easily derivatized and highly redox-tunable category of RA ligand and emphatically warrant further investigation.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02342"},"PeriodicalIF":3.7,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135936","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coordination Chemistry of Phosphinidene Stabilized by Mesoionic N-heterocyclic Carbene and Catalysis.","authors":"Biplab Gope, Nimisha Gautam, Satadru Dutta, Subir Maji, Swadhin K Mandal","doi":"10.1002/chem.202502402","DOIUrl":"https://doi.org/10.1002/chem.202502402","url":null,"abstract":"<p><p>Abnormal N-heterocyclic carbene-stabilized phosphinidene, a class of low-valent phosphorus compounds, has been recently stabilized by an isolated abnormal NHC. However, its coordination chemistry with various metal ions remained unexplored. Herein, we have explored the coordination chemistry of a mesoionic N-heterocyclic phosphinidene (mNHP,1), stabilized by an abnormal N-heterocyclic carbene (aNHC) with various metals (Cu, Zn, and Sn) to afford trimetallic, bimetallic, and monometallic complexes, respectively. All these complexes were characterized by single-crystal X-ray diffraction studies. We have also explored the catalytic activity of one of these complexes for alkynylation of trifluoromethyl ketones and found that mNHP (1)-bound trimetallic Cu-complex is an excellent catalyst for this reaction with up to 97% isolated yield under low catalyst loading (3 mol%).</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02402"},"PeriodicalIF":3.7,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Products of the Phenyl Radical (C6H5, X2A1) - Acetylene (C2H2, X1Σg+) Reaction in the 800-1,200 K Temperature Range.","authors":"Oleg V Kuznetsov, Mikhail M Evseev, Iakov A Medvedkov, Georgiy I Tolstov, Nikolay A Khvatov, Ivan O Antonov, Ralf I Kaiser, Alexander M Mebel, Valeriy N Azyazov","doi":"10.1002/chem.202502477","DOIUrl":"https://doi.org/10.1002/chem.202502477","url":null,"abstract":"<p><p>A pulsed flow high-temperature microreactor in tandem with vacuum ultraviolet photoionization (VUV PI) reflectron time-of-flight mass spectrometry (Re-TOF-MS) was employed to determine branching ratios of key product channels of the reaction of the phenyl radical (C₆H₅) with acetylene (C₂H₂) highlighting the role of the Hydrogen Abstraction - C₂H₂ Addition (HACA) mechanism at temperatures of 800-1,200 K. Temporal profiles of m/z = 26 (C₂H₂ ⁺), 30 (NO⁺), 52 (C₄H₄ ⁺), 77 (C₆H₅ ⁺), 78 (C₆H₆ ⁺), 102 (C₆H₅C₂H⁺), 103 (C₆H₅C₂H₂ ⁺), 107 (C₆H₅NO⁺), 128 (C₁₀H₈ ⁺), and 154 (C₁₂H₁₀ ⁺) were recorded and characterized within a molecular beam. From the time profiles of the ion signals and Computational Fluid Dynamics (CFD) calculations in the transient mode, zones of the molecular beam corresponding to the open valve duration time were identified. The gas velocity along the microreactor tube axis with the opened valve is strongly influenced by the backing pressure (p) in front of the nozzle and appears to be subsonic for p = 100 Torr and supersonic for p ≥ 300 Torr. The main quantified finding is that phenylacetylene (C₆H₅C₂H) constitutes the dominant product, accounting for up to 91% of consumed phenyl radicals at 1,200 K, whereas naphthalene (C₁₀H₈) formation is favored at lower temperatures and higher pressures, peaking at the yield of 53% (800 K, 300 Torr). The observed temperature and pressure dependence of naphthalene and phenylacetylene yields are consistent with the HACA mechanism.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02477"},"PeriodicalIF":3.7,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Terminal Selective Arylation of Inert Alkanes via Radical-Organometallic Crossover.","authors":"Shijin Yu, Drew M Hood, Martin P Pauze, Julian G West","doi":"10.1002/chem.202502367","DOIUrl":"10.1002/chem.202502367","url":null,"abstract":"<p><p>Selectivity is an essential part of organic synthesis and key to synthetic efficiency, where it can help reduce energy requirements for product separation, purification, and disposal of low value by-products. However, selectivity is challenging to achieve in hydrocarbon molecules, with C─H functionalization of alkanes almost invariably leading to a complex mixture of products favoring branched isomers and linear selectivity remaining elusive. Herein we report a mild and direct method that combines photo-hydrogen atom transfer (photo-HAT) and nickel catalyzed organometallic chainwalking chemistry to give the first highly linear selective arylation reaction starting from inert alkanes. Key to success is crossover from a radical to organometallic chainwalking mechanism permitted by a monodentate lutidine ligand, allowing an unselective photo-HAT step to be funneled regioconvergently to form the linear arylation product for a variety of alkanes. This result is in sharp contrast to the unselective formation of branched products using bidentate ligands and demonstrates monodentate heterocycles to be a privileged ligand class for selective C─H functionalization. Preliminary mechanistic experiments are consistent with the radical-organometallic crossover mechanism and support it as an important step toward controllable and selective functionalization of simple hydrocarbons.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02367"},"PeriodicalIF":3.7,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12465511/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tautomerism-Coupled Self-Assembly and Transformations of Iminopyrrole Metallacages.","authors":"Jakub Sukiennik, Aleksandra Sarwa, Jędrzej P Perdek, Miłosz Siczek, Bartosz Szyszko","doi":"10.1002/chem.202502714","DOIUrl":"https://doi.org/10.1002/chem.202502714","url":null,"abstract":"<p><p>Four discrete metallacages were obtained from the condensation of 2,5-diformylpyrrole and tren in the presence of Zn(II). The structures differed in nuclearity, size, and symmetry, with the number of templating cations playing a key role in defining the properties of the architecture. The diiminopyrrole coordination motif, a fundamental structural feature of assemblies, undergoes tautomerization in certain cases, yielding an iminoaminoazafulvene, which alters the assembly. The controlled interconversion between bi-, tetra-, and dodecanuclear cages was achieved through simple stimuli, highlighting the dynamic nature of these assemblies.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02714"},"PeriodicalIF":3.7,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrogen-Bonded Organic Framework Membranes: Emerging Nanofluidic Platforms for Gas Separation.","authors":"Huijie Wang, Yao Zhang, Jia-Ni Shui, Hao Sun, Chen Wang","doi":"10.1002/chem.202502541","DOIUrl":"https://doi.org/10.1002/chem.202502541","url":null,"abstract":"<p><p>The development of efficient and sustainable gas separation technologies is crucial for addressing global challenges in energy and the environment. Membrane separation technology, as an innovative, energy-saving, and highly efficient approach, offers an effective solution to these challenges. High-performance membranes materials serve as the core component enabling advanced and efficient membrane separation. Notably, hydrogen-bonded organic frameworks (HOFs) represent an emerging class of crystalline porous membrane materials formed through intermolecular hydrogen bonds between organic or metal-organic building units. The unique advantages of these materials, including moderate synthesis conditions, high crystallinity, and easy repairability and renewability, make them ideal porous membrane materials. This review comprehensively examines recent advances in HOF gas separation membranes. We objectively outline fabrication approaches and material design principle, including development prospects and preparation techniques for HOF separation membranes. We then systematically evaluate the current application status of HOF membranes in gas separation. Finally, future application potentials are projected, and challenges to be addressed in HOF gas separation are discussed.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02541"},"PeriodicalIF":3.7,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of Fully Exposed Pt Nanoparticles on a 2D Mesoporous Graphitic Nanocarbon Framework for the Oxygen Reduction Reaction.","authors":"Yuwei Deng, Qing Long, Yifan Gao, Kefei Chen, Hongyuan Sheng, Yajun Wang, Angang Dong","doi":"10.1002/chem.202502105","DOIUrl":"https://doi.org/10.1002/chem.202502105","url":null,"abstract":"<p><p>The durability of proton-exchange membrane fuel cells is often compromised by the corrosion of carbon supports in oxygen reduction reaction (ORR) cathodes under harsh operating conditions, including high oxygen concentration, elevated humidity, low pH, and high potentials. To overcome this limitation, we report the synthesis of a 2D mesoporous graphitic nanocarbon framework (MGF) via chemical etching and high-temperature graphitization. The resulting MGF features a monolayer, highly ordered nanoframe architecture that offers enhanced structural stability and conductivity. Leveraging these structural advantages, we designed fully exposed Pt nanoparticles anchored on the MGF (Pt@MGF) as a model system to investigate the interplay between graphitization degree, pore architecture, and electrocatalytic performance. Among the variants, Pt@MGF-1200, synthesized at 1200 °C, demonstrates optimized mesopore confinement and strong Pt-carbon interactions. This results in superior electrochemical durability and ORR activity, positioning Pt@MGF-1200 as a promising alternative to conventional Pt/C catalysts.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e02105"},"PeriodicalIF":3.7,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}