{"title":"Functionalized Thorium-Based Metal-Organic Frameworks for the Photocatalytic Oxidation of 1, 5-Dihydroxynaphthalene.","authors":"Hui Zhou, Ran-Wei Zhang, Xiao-Yue Pan, Shi-Yan Ai, Zi-Wei Cui, Pengfei Wu, Qing Huang, Dan Tian","doi":"10.1002/chem.202500065","DOIUrl":"https://doi.org/10.1002/chem.202500065","url":null,"abstract":"<p><p>It is still a challenging task to rationally design metal-organic framework (MOF) crystal catalysts with excellent light absorption and charge transfer for efficient photocatalytic reactions. In this work, the hexanuclear thorium clusters, porphyrin derivative ligands, and linear carboxylic acid ligands were assemed into Th-based metal-organic frameworks (Th6-TCPP, Th6-Co-TCPP, and Th6-Ni-TCPP) by the mixed ligand method. The three prepared MOF crystals were applied in the photocatalytic oxidation of 1, 5-dihydroxynaphthalene (1, 5-DHN) for the synthesis of juglone. Among them, Th6-TCPP exhibited optimum photodynamic activity for production of reactive oxygen species. Under lillumination, Th6-TCPP resulted in photochemical reaction conversion rate up to 95% for 9, 10-diphenylanthracene (DPA) and 54.5% for 1, 5-DHN. The good catalytic effect was attributed to the large conjugate system of porphyrin and the enhanced photosensitivity of bipyridine.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500065"},"PeriodicalIF":3.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514200","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":"Simultaneous Construction of Axial and Central Stereogenicity by Cobalt-Catalyzed Stereoconvergent Reductive Coupling of Heterobiaryl Triflates and Aldehydes.","authors":"Chuiyi Lin, Xiang Xu, Qinglei Chong, Fanke Meng","doi":"10.1002/chem.202500248","DOIUrl":"https://doi.org/10.1002/chem.202500248","url":null,"abstract":"<p><p>Catalytic stereoconvergent coupling of racemic heterobiaryl triflates and aldehydes promoted by a readily available chiral cobalt complex is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable simultaneous construction of axial and central stereogenicity through diastereo- and enantioselective dynamic kinetic transformations and introduction of a chiral fragment onto the heterobiaryl cores without the requirement of preforming stoichiometric amounts of organometallic reagents, affording densely functionalized secondary alcohols in up to 96% yield, >98:2 dr and >99.5:0.5 er. Preliminary investigations on the application of the products demonstrate their potential for serving as a new class of chiral catalysts and ligands. Mechanistic studies suggest that a dynamic kinetic stereoselective process induced by chiral cobalt catalysis is involved.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500248"},"PeriodicalIF":3.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143497530","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":"Asymmetric Amination of 1,2-Diol through Borrowing Hydrogen: Synthesis of Vicinal Amino α-Tertiary Alcohol.","authors":"Tariq Ali, Tahir Rahman, Shahida Perveen, Lingyun Wang, Ajmal Khan","doi":"10.1002/chem.202404152","DOIUrl":"https://doi.org/10.1002/chem.202404152","url":null,"abstract":"<p><p>Methods to prepare vicinal amino alcohols are important because of their presence in biologically active compounds. Despite the development of various methods for vicinal amino alcohol synthesis, C(sp3)-rich oxygen-containing β-amine compounds continue to pose great challenge. While ring-opening reaction of epoxides with amine nucleophile is the prime method for vicinal amino alcohol preparation, epoxides are highly reactive and sometimes difficult to make, resulting in drawbacks regarding selectivity of this approach. Here, we report a catalytic enantio-convergent amination of α-tertiary 1,2-diols for the efficient access to vicinal amino α-tertiary alcohols. The racemic α-tertiary 1,2-diol substrates of different alkyl/aryl or alkyl/alkyl backbone, can be converted to chiral vicinal amino a-tertiary alcohols through diphenyl phosphate-mediated RuCl3 catalysed asymmetric borrowing hydrogen (ABH) pathway. This simple ABH reaction can be scaled up to the synthesis of chiral ligands, synthetic intermediates, and other medicinally-relevant compounds. Overall, this catalytic redox-neutral procedure broadens the scope of Ru-catalysed amination of alcohols and discloses an underexplored step- and atom-economical synthetic strategy for the synthesis of vicinal amino α-tertiary alcohols and provides a practicable alternative to the present benchmark procedures.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404152"},"PeriodicalIF":3.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514193","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":"Adaptive Coordination Behavior of Bisphosphanylphosphanido-Ligands toward Group 2, 11 and 12 Metal Ions.","authors":"Dennis Langgut, Clemens Bruhn, Rudolf Pietschnig","doi":"10.1002/chem.202500406","DOIUrl":"https://doi.org/10.1002/chem.202500406","url":null,"abstract":"<p><p>A series of alkaline earth metal complexes (Mg-Ba) with the anionic ferrocenylene-bridged bisphosphanylphosphanide ligand [Fe(C5H4PC4H9)2P]- has been prepared by metalation of the corresponding bisphosphanylhydrophosphane (Fe(C5H4PC4H9)2PH). The resulting complexes have been characterized by multinuclear NMR spectroscopy and SC-XRD. Furthermore, the closely related zinc phosphanide, and rare, mononuclear coinage metal phosphanides were synthesized and investigated for comparison. The range of coordination modes observed for the phosphanide ligand included mono-, bi-, and tridentate modi and their respective combinations, whereas no μ2-bridging of the phosphanide center has been observed. The value of the 1JPP coupling constant was found to be a good probe to track the coordination motif consistent with the situation in solid state.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500406"},"PeriodicalIF":3.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143497493","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}
Dr. Clémence Simon, Dr. Mingxiang Zhu, Prof. Dr. Cédric Lion, Dr. Corentin Spriet, Maxence Hemry, Prof. Dr. Godfrey Neutelings, Prof. Dr. Samir Messaoudi, Prof. Dr. Christophe Biot
{"title":"Cover Feature: Design and Synthesis of Thioglycosylated Monolignol Dual Probes for Bioimaging of Lignin Biosynthesis (Chem. Eur. J. 12/2025)","authors":"Dr. Clémence Simon, Dr. Mingxiang Zhu, Prof. Dr. Cédric Lion, Dr. Corentin Spriet, Maxence Hemry, Prof. Dr. Godfrey Neutelings, Prof. Dr. Samir Messaoudi, Prof. Dr. Christophe Biot","doi":"10.1002/chem.202581202","DOIUrl":"https://doi.org/10.1002/chem.202581202","url":null,"abstract":"<p><b>The Cover Feature</b> highlights the design and synthesis of thioglycosylated monolignol probes that were developed for the biological imaging of lignin biosynthesis. These innovative probes mimic monolignol glucosides (MLGs), which are hypothesized to play a role in monolignol transport and storage, though their exact function in lignin biosynthesis remains unclear. By incorporating a thioglycosyl moiety, these probes enable selective metabolic incorporation and facilitate the tracking of lignin biosynthesis in vivo. More information can be found in the Research Article by S. Messaoudi, C. Biot and co-workers (DOI: 10.1002/chem.202404117).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 12","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581202","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489886","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}
Takefumi Kuranaga, Ai Koyama, Junta Asano, Takumi Matsumoto, Hideaki Kakeya
{"title":"Twisted Amide-Mediated Synthesis and Rapid Structure-Activity Relationship Study of Medium-Sized Cyclic Peptides.","authors":"Takefumi Kuranaga, Ai Koyama, Junta Asano, Takumi Matsumoto, Hideaki Kakeya","doi":"10.1002/chem.202500331","DOIUrl":"10.1002/chem.202500331","url":null,"abstract":"<p><p>Medium-sized cyclic peptides are expected to be ideal drug leads because these peptides combine the advantages, while compensating for the disadvantages, of small molecules and antibodies. Although medium-sized peptides can be produced by chemical synthesis, two major problems, namely (i) Cα-epimerization during C-terminal modification and (ii) side reactions in the cyclization, remain to be solved. These issues have hampered the synthesis of pure materials for bioassays, making it difficult to accomplish accurate structure-activity relationship (SAR) studies. Herein, we report an efficient synthesis of medium-sized cyclic peptides based on the twisted amide-mediated amidation strategy. First, a variety of linear peptides were synthesized by the \"inverse\" peptide synthesis and fragment coupling. Second, the C-terminus of the linear peptides were converted to twisted amides, which were then reacted with a variety of α-amino acyl sulfonamides, realizing the rapid C-terminal diversification of peptides. Finally, the resulting linear peptides were cyclized by the intramolecular twisted amide-mediated amidation to afford stereochemically pure cyclic peptides. Using this strategy, total synthesis of acyl-surugamide A, the stereoselective synthesis of 13 non-natural analogs, and the discovery of potent antimicrobial/antifungal peptides beyond the natural product were also achieved.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500331"},"PeriodicalIF":3.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143497532","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":"Front Cover: DiQuinoline-MonoQuinazoline: A Flat Proton Binder and its Application as a Polyaromatic Hydrocarbon Scavenger and G4 Ligand (Chem. Eur. J. 12/2025)","authors":"Taiga Karimata, Wei Xu, Naoya Kumagai","doi":"10.1002/chem.202581201","DOIUrl":"https://doi.org/10.1002/chem.202581201","url":null,"abstract":"<p><b>The Front Cover</b> shows an artistic ball-and-stick representation of the DiQuinoline-MonoQuinazoline (<b>Q2Qz1</b>) molecule with a central atom-sized cavity. The cavity is surrounded by lone-pair orbitals from three nitrogen atoms. The quinazoline unit also features an additional nitrogen lone-pair orbital located at the periphery of the planar macrocycle. More information can be found in the Research Article by N. Kumagai and co-workers (DOI: 10.1002/chem.202404335).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 12","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489885","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}
Vyacheslav V. Diev, Yunlong Zou, Denis Kondakov, Glenn P. A. Yap
{"title":"Cover Feature: A Hybrid BN-Doped Nanographene with Narrow Emission Bandwidths for OLEDs (Chem. Eur. J. 12/2025)","authors":"Vyacheslav V. Diev, Yunlong Zou, Denis Kondakov, Glenn P. A. Yap","doi":"10.1002/chem.202581204","DOIUrl":"https://doi.org/10.1002/chem.202581204","url":null,"abstract":"<p><b>The Cover Feature</b> depicts a hybrid BN-doped nanographene, its emission spectrum with its extraordinarily narrow main peak, and a solid-state organization diagram. Reminiscent of the natural purity of the landscape of Delaware (background), the state where the molecule was synthesized, emission color purity is essential for high-performance organic light emitting diodes. Based on screening efforts, the Research Article by V. V. Diev and co-workers (DOI: 10.1002/chem.202404078) describes the synthesis, characterization and OLED evaluation of a BN-containing candidate.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":"31 12","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581204","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489889","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":"Sulfide Synthesis via A Bioinspired C-S σ-Bond Metathesis.","authors":"Youwei Xie, Hongmei Liu, Yuzhu Zheng, Ke-Lin Xian, Qi-Qi Hu, Rong-Zhen Liao","doi":"10.1002/chem.202500153","DOIUrl":"https://doi.org/10.1002/chem.202500153","url":null,"abstract":"<p><p>In this manuscript, inspired by the natural S-adenosylmethionine (SAM) cycle, we devised a mixed σ-bond metathesis between the (sp3)C-S bond of organic sulfides with the C-O bond of alcohols. This reaction is mediated by a readily available and operationally facile mixture of AlCl3 and ZnI2, which allows fast access to various challenging organic sulfides by directly editing the (sp3)C-S bond of easily available ones. Like multiple bond metathesis, this method could also be rendered intramolecular and extended to ether (sp3)C-O bond metathesis as well as amine (sp3)C-N bond metathesis to provide saturated heterocycles such as cyclic thioethers, cyclic ethers, as well as cyclic amines. Mechanistic experiments and DFT calculations were carried out to show a high level of resemblance to the natural SAM cycle. We anticipate this bioinspired design of C-S/C-O metathesis will infuse the area of a σ-bond metathesis with more insights and provide opportunities for further advances in areas that have been facilitated by traditional C-X bond forming reactions.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500153"},"PeriodicalIF":3.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143490262","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}
Shweta Gaikwad, Argha Bhattacharjee, Elizabeth Elacqua
{"title":"Cooperative Photoredox Catalysis Under Confinement.","authors":"Shweta Gaikwad, Argha Bhattacharjee, Elizabeth Elacqua","doi":"10.1002/chem.202404699","DOIUrl":"https://doi.org/10.1002/chem.202404699","url":null,"abstract":"<p><p>Photoredox catalysis has emerged as a potent means to conduct synthetic chemistry. Leveraging light to achieve challenging organic transformations has led to many developments, both of fundamental and industrial nature. Despite their potency, photoredox processes are inherently diffusion controlled, which can limit their ability to enable both reactivity and selectivity. Relevant to this is the idea of colocalizing cocatalysts in architectures that enable spatial proximity, promoting 'catalysis under confinement.' In this Concept review, we summarize recent designs and advancements using well-defined heterogeneous and homogeneous frameworks that enable dual photoredox catalysis, such as metal-organic frameworks, heterogeneous organic polymeric systems, and single-chain polymer nanoparticles (SCNPs). These advances generally stem from the material's inherent ability to enforce catalyst communication, typically resulting in expedient radical, electron, or energy transfer that accelerates reactivity. Whereas heterogeneous systems are comprehensively investigated, the design space arising from the modularity and versatility of a SCNP is quite large making the recyclable platform an intriguing candidate to investigate for confinement-enabled photoredox catalysis. We expect that both heterogeneous and homogeneous platforms systems detailed herein will continue to exhibit superior performance, while underscoring the importance of confinement to tackle diffusion-limited reactions.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404699"},"PeriodicalIF":3.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143497522","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}