Simon Sengupta, Maximillian Broek, Phil Köhler, Matthias Westerhausen
{"title":"Synthesis of Heteroleptic Amidinato Calcium Halides via the In-Situ Grignard Addition Method (iGAM) Complementing the Metalation of Amidines.","authors":"Simon Sengupta, Maximillian Broek, Phil Köhler, Matthias Westerhausen","doi":"10.1002/chem.202500210","DOIUrl":"10.1002/chem.202500210","url":null,"abstract":"<p><p>The in-situ Grignard addition method adds intermediately prepared organo alkaline-earth metal halides onto a suitable substrate. Here, freshly rasped calcium and the carbodiimide R'─N═C═N─R' (R' = SiMe<sub>3</sub>, iPr) are suspended in THF at room temperature and then an organyl halide R─X (X = Br, I) is added. Within several hours, intermediately formed R─Ca─X adds onto the carbodiimide yielding the corresponding thf adducts of the amidinato calcium halide {(R'N)<sub>2</sub>C─R}CaX. Suitable organyl halides besides aryl iodide are methyl and ethyl halide whereas bulkier isopropyl and tert-butyl iodides give very low yields.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500210"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661702","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}
Nidal Saleh, Valerio Zullo, Estefanía Sucre-Rosales, Lorenzo Arrico, Francesco Zinna, Gennaro Pescitelli, Céline Besnard, Eric Vauthey, Jerome Lacour
{"title":"Tethered Enantiopure Boramidines for Advanced Chiroptical Studies.","authors":"Nidal Saleh, Valerio Zullo, Estefanía Sucre-Rosales, Lorenzo Arrico, Francesco Zinna, Gennaro Pescitelli, Céline Besnard, Eric Vauthey, Jerome Lacour","doi":"10.1002/chem.202500490","DOIUrl":"https://doi.org/10.1002/chem.202500490","url":null,"abstract":"<p><p>Boramidines are promising chromophores capable of circularly polarized luminescence (CPL). The synthesis, characterization, and photophysical analysis of novel BINOL- and H8-BINOL-tethered boramidines 1 and 2 are reported, leveraging the chiral perturbation strategy for CPL material design. These enantiopure compounds, prepared in a concise three-step synthesis, exhibit high fluorescence quantum yields ϕ (up to 95% in N2-saturated solutions) and luminescence dissymmetry factors (|glum| ~10-3). Transient absorption spectroscopy and quantum-chemical calculations provide insight into their singlet-triplet spin-orbit coupling and intersystem crossing mechanisms.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500490"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143655635","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":"Chiral Porous Organic Polymers (CPOPs): Design, Synthesis and Applications in Asymmetric Catalysis.","authors":"Keshaba Nanda Parida, Chetna Yadav, Swati Jindal, Parag Tamuly, Yashwant D Vankar, Jarugu Narasimha Moorthy","doi":"10.1002/chem.202404525","DOIUrl":"https://doi.org/10.1002/chem.202404525","url":null,"abstract":"<p><p>Since the recognition of the area of asymmetric synthesis in 2000, there has been a tremendous focus on the development of heterogeneous catalysts for asymmetric synthesis. Porous organic polymers (POPs) have emerged in recent years as inextricable materials of high physicochemical and hydrolytic stabilities, permitting infinite possibilities to modulate and tune reactivity, engineer porosity, regulate spatial environments and pore attributes, and manoeuver material transport. With a diligent design of building blocks and the exploitation of organic reactions judiciously, the synthesis of POPs with BET surface areas of the order of a few thousand cm3/g has been demonstrated. The incorporation of reactive functional groups and chiral centres into the porous matrices of polymers offers opportunities to conduct asymmetric synthesis. Very high enantioselectivities of the order of 99% ee have been exemplified in the reactions mediated by chiral POPs (CPOPs). The design-driven tunability of POPs allows the development of catalytic materials for targeted applications in a tailor-made fashion. This review, while placing the development of chiral materials for asymmetric synthesis in the right perspective, delves into different design principles to pave the way for continued research on futuristic CPOP materials by a creative design, limited by one's imagination, for heretofore unprecedented results.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404525"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661684","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}
Zhenqiang Xia, Dasharath Kondhare, Sushma Deshmukh, Somnath Chandankar, Peter Leonard
{"title":"Bioorthogonal Functionalization in the Minor Groove of DNA: Inverse-Electron Demand Diels Alder Reactions with Cyclopropenyl and Heptenoyl Protected 2-Amino-2'-deoxyadenosine as Target Site.","authors":"Zhenqiang Xia, Dasharath Kondhare, Sushma Deshmukh, Somnath Chandankar, Peter Leonard","doi":"10.1002/chem.202500529","DOIUrl":"https://doi.org/10.1002/chem.202500529","url":null,"abstract":"<p><p>Bioorthogonal functionalization in the minor groove of DNA with protected 2-amino-2'-deoxyadenosine (2-amino-dA, 1) as target site is described. Cyclopropene and heptene as part of 2-aminoacyl protecting groups served as dienophiles in inverse-electron demand Diels-Alder (iEDDA) reactions with 3,6-dipyridyl-1,2,4,5-tetrazine as diene. For the purpose, bis-protection of 1 with cyclopropenyl and heptenoyl groups was conducted. Selective removal of the 6-amino protecting groups gave mono-protected 1. 2-Amino-dA pyridazine conjugates were accessed by iEDDA cycloaddition with tetrazine. Second order rate constants disclosed faster reaction kinetics for cyclopropenyl than for heptenoyl 2-amino-dA. To access protected oligonucleotides, phosphoramidites prepared from bis-protected 2-amino-dA were used in standard solid-phase synthesis. 2-Amino protecting groups were retained using mild deprotection conditions. Hybridization experiments disclosed increased duplex stability when protected 2-amino-dA-dT pairs replaced 1-dT pairs. Mismatch discrimination of cyclopropenyl and heptenoyl 2-amino-dA was superior to 2-amino-dA. iEDDA reactions on protected oligonucleotides furnished oligonucleotide pyridazine conjugates. In base pairs with dT, 2-amino-dA pyridazine conjugates connected by a short rigid cyclopropenyl ring led to reduced thermal stability, whereas pyridazine conjugates attached by a long flexible linker retained duplex stability. The findings of this investigation pave the way for functionalization and labelling in the minor groove of DNA using copper free iEDDA cycloaddition.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500529"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661682","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}
Mengtian Lu, Tianye Zhang, Yue Yang, Xin Lin, Jin Huang, Yuan Sun, Tiedong Sun
{"title":"MXene Loaded with Cu(2-x)Se Nanozyme for Nanocatalytic Tumor Therapy.","authors":"Mengtian Lu, Tianye Zhang, Yue Yang, Xin Lin, Jin Huang, Yuan Sun, Tiedong Sun","doi":"10.1002/chem.202500574","DOIUrl":"https://doi.org/10.1002/chem.202500574","url":null,"abstract":"<p><p>Traditional tumor treatments have certain limitations which have serious negative effects, such as the difficulty in cutting out tumors, the damage to normal tissues, and complications. Ordinary nanozymes generally have low catalytic activity and require higher doses for treatment, which can increase the toxicity and side effects. Here, we designed a Cu(2-x)Se-loaded on MXene, which can catalyze the conversion of the overexpressed hydrogen peroxide into O2 and -OH in cancer cells by Cu(2-x)Se with the catalase (CAT)-like activity and peroxidase (POD) activity, which can effectively alleviate the tumor microenvironment (TEM) hypoxia, as well as degrading the overexpressed glutathione (GSH) and killing the tumor cells to a large extent. At the same time, we used Nanozyme-Carrier Interface Modulation (NCIM): by regulating the interface interaction between nanozymesand carrier materials , the catalytic activity of nanozymes and the photothermal performance of the support were optimized. This regulation can be achieved by adjusting the mass ratio of nanozymes to carriers, surface modification, etc. to improve the performance of the composites. Dual enzyme-active nanozymes loaded with MXene provide a way to synergies catalytic and photothermal therapies, which are considered to be promising materials for future development in the field of nanocomposites for disease treatment.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500574"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661697","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}
Maren Neubrand, Jessica Stubbe, Richard Rudolf, Robert R M Walter, Maite Nößler, Biprajit Sarkar
{"title":"Activation and Fixation of Atmospheric CO<sub>2</sub> through a 1,2,3-Triazole-Based Mesoionic Carbene-Borane Adduct.","authors":"Maren Neubrand, Jessica Stubbe, Richard Rudolf, Robert R M Walter, Maite Nößler, Biprajit Sarkar","doi":"10.1002/chem.202403942","DOIUrl":"10.1002/chem.202403942","url":null,"abstract":"<p><p>Capturing atmospheric CO<sub>2</sub> and converting it to valuable chemicals are important goals in contemporary science. We present here a simple, transition metal-free triazolylidene-borane adduct that can capture atmospheric CO<sub>2</sub> and convert it to formate. Several key intermediates were isolated and characterized by a combination of multinuclear NMR spectroscopy, IR spectroscopy and single crystal X-ray diffraction. A first closed cycle for the conversion of CO<sub>2</sub> to formic acid by using the aforementioned triazolylidene-borane compound is presented as well.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403942"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143655715","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}
Chiara Rosso, Rebecca Birolo, Angelo Gallo, William T Franks, Emanuele Priola, Michele R Chierotti, Roberto Gobetto
{"title":"Exploring Tyramine's Role in the Formation of Supramolecular Adducts with Nonsteroidal Anti-Inflammatory Drugs.","authors":"Chiara Rosso, Rebecca Birolo, Angelo Gallo, William T Franks, Emanuele Priola, Michele R Chierotti, Roberto Gobetto","doi":"10.1002/chem.202500080","DOIUrl":"https://doi.org/10.1002/chem.202500080","url":null,"abstract":"<p><p>In pharmaceutical crystal engineering, salification and co-crystallization are well-established strategies to enhance the physicochemical properties of non-steroidal anti-inflammatory drugs (NSAIDs), which typically exhibit low aqueous solubility. This study introduces three new multicomponent crystalline systems of NSAIDs (S-naproxen, flurbiprofen, and ketoprofen) with the coformer tyramine, designed using knowledge-based methods. Additionally, a new polymorph of the diflunisal-tyramine system, synthesized via mechanochemical techniques, is reported. The new multicomponent systems were thoroughly characterized using solid-state NMR and single-crystal X-ray diffraction. Aqueous solubility tests conducted through solution 1H NMR experiments revealed increased equilibrium solubility for all samples, highlighting the efficacy of crystal engineering in modulating the physicochemical properties of drugs.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500080"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143655727","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":"Catalytic Performances of Carbon-Based Tetrel Bond Catalysis by Density Functional Theory and Machine Learning.","authors":"Yanjiang Wang, Wen-Kai Chen, Yanli Zeng","doi":"10.1002/chem.202500625","DOIUrl":"10.1002/chem.202500625","url":null,"abstract":"<p><p>The non-covalent interaction catalysis has been widely developed and applied in organocatalysis for its green and economical characteristics. In recent years, the carbon-based tetrel bonds have been successfully applied in organocatalysis. In this work, the structure-property relationship of carbon-based tetrel bond catalysts is established by utilizing density functional theory (DFT) and machine learning (ML). Taking the Michael addition reaction as an example, the reaction mechanism and new insight into the catalytic active site are introduced based on the DFT-calculated results. The bowl-like 1,1-dicyano-3,3-dicarbonylcyclopropane (DCDC) unit based σ-hole is much more important than the 1,1,2,2-tetracyanocyclopropane (TCCP) unit in tetrel bond catalysts. Introducing electron-withdrawing groups into catalysts significantly enhances the catalytic activity and provides a new strategy for designing efficient catalysts. Furthermore, the construction and evaluation of ML models demonstrate their potential in predicting the catalyst performance, offering a new protocol for fast prediction of the catalytic performance of tetrel bond catalysts.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500625"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143655721","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}
Jie Chen, Wenjing Wu, Yongzhen Peng, Zheng Fang, Yujing Hu, Kai Guo
{"title":"Ene-Reductases-Catalyzed Non-Natural Reactions.","authors":"Jie Chen, Wenjing Wu, Yongzhen Peng, Zheng Fang, Yujing Hu, Kai Guo","doi":"10.1002/chem.202500539","DOIUrl":"10.1002/chem.202500539","url":null,"abstract":"<p><p>Flavin-dependent ene-reductases (EREDs), members of the Old Yellow Enzyme (OYE) superfamily, are highly efficient biocatalysts primarily known for catalyzing the asymmetric reduction of activated alkenes. Beyond this native function, the chemical versatility of the flavin cofactor and the sophisticated architecture of their protein structures enable EREDs to exhibit catalytic multifunctionality. The catalytic promiscuity not only highlights the adaptability of these enzymes but also expands their potential to broaden the scope of enzyme-catalyzed reactions in organic synthesis. Given the inherent challenges associated with discovering novel enzyme activities, such catalytic promiscuity of EREDs offers a promising pathway for expanding their applications. This mini-review provides a comprehensive overview of the catalytic multifunctionality of flavin-dependent EREDs, with a particular focus on their \"non-natural\" functionalities in organic synthesis. This review is primarily divided into two main sections: hydride-dependent reactions and hydride-independent reactions. By highlighting these unconventional biocatalytic pathways, we aim to inspire further exploration into the untapped potential of EREDs and their role in advancing synthetic chemistry.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500539"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143655724","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}
Francesco Gabriele, Roberta Colaiezzi, Andrea Lazzarini, Franco D'Orazio, Valeria Daniele, Giuliana Taglieri, Nicoletta Spreti, Marcello Crucianelli
{"title":"The Use of Deep Eutectic Solvents for the Synthesis of Iron Oxides Nanoparticles: A Driving Force for Materials Properties.","authors":"Francesco Gabriele, Roberta Colaiezzi, Andrea Lazzarini, Franco D'Orazio, Valeria Daniele, Giuliana Taglieri, Nicoletta Spreti, Marcello Crucianelli","doi":"10.1002/chem.202500089","DOIUrl":"10.1002/chem.202500089","url":null,"abstract":"<p><p>In this study, we explored the use of Deep Eutectic Solvents (DESs) as a green and sustainable alternative for the synthesis of Iron Oxide Nanoparticles (IONs). Six different binary mixtures of Hydrogen Bond Acceptors (HBAs) and Donors (HBDs) were prepared and thoroughly characterized to investigate how their components and physicochemical properties influence the structure, morphology, and magnetic properties of the resulting IONs. In addition, the role of DESs was assessed using ATR-MIR spectroscopy, providing insights into HBA-HBD interactions with iron precursors. The study highlights the critical role of DES constituents, particularly the interactions between HBAs and HBDs, in directing nanoparticle size, structure, and morphology. Indeed, our results demonstrate that the choice of DES significantly impacts the crystalline phase of iron oxide nanoparticles, yielding either magnetite (Fe₃O₄) or hematite (α-Fe₂O₃). These findings established a robust framework for leveraging DES in nanomaterial synthesis, paving the way for more environmentally friendly approaches in diverse industrial and scientific applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500089"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661704","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}