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Abundant Transition Metal Based Photocatalysts for Red Light Driven Photocatalysis.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-26 DOI: 10.1002/chem.202500365
Narayan Sinha, Nitish Kumar, Tanu Sharma, Nirbhay Thakur, Rahul Jain
{"title":"Abundant Transition Metal Based Photocatalysts for Red Light Driven Photocatalysis.","authors":"Narayan Sinha, Nitish Kumar, Tanu Sharma, Nirbhay Thakur, Rahul Jain","doi":"10.1002/chem.202500365","DOIUrl":"https://doi.org/10.1002/chem.202500365","url":null,"abstract":"<p><p>Photocatalysis emerges as an efficient and versatile tool for the preparation of organic compounds via development of new methodologies and new photosensitizers. Mostly UV and blue light irradiation are used for such reactions. Red light is low energy light, it is less harmful and has more penetration depth. Hence red light driven photocatalysis would be more suitable for preparing value added products. Red absorbing photosensitizers are mostly based on rare and expensive metals. In this review, we describe the recent developments on Earth-abundant transition metal-based photosensitizers (W(0), Mo(0), Cr(0), Fe(III), Cu(I), Zn(II)) and their applications in red light driven photocatalysis. Photocatalysis using both electron transfer and energy transfer processes are discussed. Three different red light induced reactions such as direct monophotonic excitation, sensitized triplet-triplet annihilation upconversion (sTTA-UC) and dual red light photocatalysis are presented. Various organic transformations such as reductive dehalogenation and detosylation, reduction of diazonium salts, C-C coupling via C-H activation, oxidation of aryl boronic acids to phenols, polymerization reactions, cross dehydrogenative couplings, α-cyanation of tertiary amines, Barton decarboxylation have been carried out using abundant photosensitizers and red light.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500365"},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707823","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}
引用次数: 0
Cover Feature: Heterogeneous Catalytic Oxidations with In Situ-Generated Hypervalent Iodine-Based Porous Organic Polymers (Chem. Eur. J. 18/2025)
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-26 DOI: 10.1002/chem.202581802
Parag Tamuly, Keshaba Nanda Parida, Stéphane Quideau, Jarugu Narasimha Moorthy
{"title":"Cover Feature: Heterogeneous Catalytic Oxidations with In Situ-Generated Hypervalent Iodine-Based Porous Organic Polymers (Chem. Eur. J. 18/2025)","authors":"Parag Tamuly,&nbsp;Keshaba Nanda Parida,&nbsp;Stéphane Quideau,&nbsp;Jarugu Narasimha Moorthy","doi":"10.1002/chem.202581802","DOIUrl":"https://doi.org/10.1002/chem.202581802","url":null,"abstract":"<p><b>The Cover Feature</b> illustrates the alliance of polymer and hypervalent iodine chemistries for green and sustainable chemical transformations. Rationally designed porous organic polymers (POPs), which feature a twisted biaryl core and contain <i>ortho</i>-iodobenzoic acid moieties, generate in situ hypervalent iodine(V) IBX-like organocatalysts when treated with Oxone<sup>®</sup> and facilitate heterogeneous oxidations efficiently. More information can be found in the Research Article by J. N. Moorthy and co-workers (DOI: 10.1002/chem.202403402).\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 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581802","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698859","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}
引用次数: 0
A Biocompatible Cinchonine-Based Catalyst for the CO2 Valorization into Oxazolidin-2-ones Under Ambient Conditions.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-26 DOI: 10.1002/chem.202500473
Lucia Invernizzi, Caterina Damiano, Emma Gallo
{"title":"A Biocompatible Cinchonine-Based Catalyst for the CO<sub>2</sub> Valorization into Oxazolidin-2-ones Under Ambient Conditions.","authors":"Lucia Invernizzi, Caterina Damiano, Emma Gallo","doi":"10.1002/chem.202500473","DOIUrl":"https://doi.org/10.1002/chem.202500473","url":null,"abstract":"<p><p>A metal-free, biocompatible catalyst for the cycloaddition of CO<sub>2</sub> to N-alkyl aziridines was easily obtained by protonating the natural and nontoxic alkaloid (+)-cinchonine. This bifunctional catalytic system promoted the synthesis of the desired products under very mild experimental conditions (room temperature and atmospheric CO<sub>2</sub> pressure) and without the aid of any cocatalyst. No specific equipment is required, making the procedure practical for application in any laboratory. The high synthetic value of this methodology can be attributed to the combination of excellent regioselectivity in oxazolidinone synthesis and the remarkable chemical stability of the catalyst, which can be recycled and reused for at least three consecutive cycles without any significant loss of activity.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500473"},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707822","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}
引用次数: 0
Construction of Novel Chiral NPN Ligands and the Application in Gold(I)-catalyzed Asymmetric Cycloaddition Reactions.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-26 DOI: 10.1002/chem.202500465
Yang-Wei Xia, Bing Xu, Zhanming Zhang, Junliang Zhang
{"title":"Construction of Novel Chiral NPN Ligands and the Application in Gold(I)-catalyzed Asymmetric Cycloaddition Reactions.","authors":"Yang-Wei Xia, Bing Xu, Zhanming Zhang, Junliang Zhang","doi":"10.1002/chem.202500465","DOIUrl":"https://doi.org/10.1002/chem.202500465","url":null,"abstract":"<p><p>The development of new chiral ligands has always been a significant research topic in the field of asymmetric synthesis. This paper reports a novel chiral NPN ligand (termed Xia-Phos) derived from the modification of Ming-Phos. This series of ligands possess advantages such as easy synthesis and convenient modification. Moreover, they exhibit excellent enantioselectivity in gold(I)-catalyzed asymmetric [3+3] cycloaddition reactions.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500465"},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143727281","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}
引用次数: 0
Cover Feature: Poly(Ferrocenylene Iminoborane) and the Merging of 1,1’-Ferrocenylene with p-Phenylene Iminoborane Building Blocks into Alternating Copolymers, Oligomers, and Macrocycles (Chem. Eur. J. 18/2025)
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-26 DOI: 10.1002/chem.202581804
Johannes S. Schneider, Vivien Zeh, Jonas Klopf, Philipp M. Schneider, Jonas Bachmann, Ivo Krummenacher, Holger Braunschweig, Holger Helten
{"title":"Cover Feature: Poly(Ferrocenylene Iminoborane) and the Merging of 1,1’-Ferrocenylene with p-Phenylene Iminoborane Building Blocks into Alternating Copolymers, Oligomers, and Macrocycles (Chem. Eur. J. 18/2025)","authors":"Johannes S. Schneider,&nbsp;Vivien Zeh,&nbsp;Jonas Klopf,&nbsp;Philipp M. Schneider,&nbsp;Jonas Bachmann,&nbsp;Ivo Krummenacher,&nbsp;Holger Braunschweig,&nbsp;Holger Helten","doi":"10.1002/chem.202581804","DOIUrl":"https://doi.org/10.1002/chem.202581804","url":null,"abstract":"<p><b>The Cover Feature</b> shows oligomers and polymers containing redox-active ferrocene moieties, BN units and <i>p</i>-phenylene building blocks, which are represented by the three vessels. Cyclic and linear polymers were obtained from polycondensation reactions. Electrochemical and photophysical investigations provided valuable insights into the interactions of the building blocks and the electronic communication between the ferrocene units. More information can be found in the Research Article by H. Helten and co-authors (DOI: 10.1002/chem.202404533). Cover image by Tina Schneider.\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 18","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581804","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699036","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}
引用次数: 0
Halogen Bond-Driven Ligand Displacement: Co-crystal Lattice vs Coordination Bonds.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-26 DOI: 10.1002/chem.202404784
Yury V Torubaev, Omer Shaashua, Savion Braunstein, Doron Pappo
{"title":"Halogen Bond-Driven Ligand Displacement: Co-crystal Lattice vs Coordination Bonds.","authors":"Yury V Torubaev, Omer Shaashua, Savion Braunstein, Doron Pappo","doi":"10.1002/chem.202404784","DOIUrl":"https://doi.org/10.1002/chem.202404784","url":null,"abstract":"<p><p>Coordination bonds are generally stronger than halogen bonds; however, the Jahn-Teller effect in d⁹ Cu(II) and the trans influence of the oxo-ligand in vanadyl (V=O) acetylacetonates can weaken N→Cu/V bonds, bringing them closer to the upper range of halogen bond strength. The study investigates the interactions between transition metal acetylacetonate complexes, M(acac)2(L) (M = Cu(II), V(IV)=O; L = amine ligands), and halogen bond (XB)-donor co-formers, particularly 1,4-diiodotetrafluorobenzene (1,4-DITFB). The co-crystallization experiments reveal an unusual ligand displacement phenomenon wherein the expected M(acac)2(L)·1,4-DITFB complexes fail to form, instead yielding separate M(acac)2·1,4-DITFB and L·1,4-DITFB co-crystals. Computational studies reveal that while XB interactions alone may be insufficient to disrupt the M-N coordination bond, they can induce ligand displacement when amplified by the lattice stabilization of the resulting halogen-bonded co-crystals, particularly in Jahn-Teller distorted d⁹ Cu(II) and trans-influenced V(IV)=O complexes interacting with halogen bond donors.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404784"},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707835","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}
引用次数: 0
The Role of Lithium Ions on the Solubility of K4E4 in Ethylenediamine and the Oxidation of the Zintl Anions [E4]4- (E = Ge, Sn, Pb) as well as [Ge9]4.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-26 DOI: 10.1002/chem.202500592
Thomas Friedrich Fässler, Christian E Fajman, Dominik M Dankert, Wilhelm Klein
{"title":"The Role of Lithium Ions on the Solubility of K4E4 in Ethylenediamine and the Oxidation of the Zintl Anions [E4]4- (E = Ge, Sn, Pb) as well as [Ge9]4.","authors":"Thomas Friedrich Fässler, Christian E Fajman, Dominik M Dankert, Wilhelm Klein","doi":"10.1002/chem.202500592","DOIUrl":"https://doi.org/10.1002/chem.202500592","url":null,"abstract":"<p><p>Zintl phases are excellent precursors for nine atom [E9]4- clusters, which are readily accessible by dissolution of A4E9 phases (A = Na-Rb; E = Ge- Pb) in ethylenediamine (en). In contrast, the binary alkali-metal tetrel phases of composition A4E4 are insoluble in en. Furthermore, Li cations are rarely investigated as counterions for tetrel element Zintl clusters. We report here that K4E4 comprising [E4]4- polyanions (E = Ge, Sn, Pb), which are insoluble in en, readily dissolves in en in the presence of lithium ions and the four atomic polyanions [E4]4- are oxidized to nine-atom [E9]4- clusters during dissolution. We isolated crystals with exclusively Li counterions such as [Li(en)2.5]4[Ge9] and [Li(en)2]4[E9] (E = Sn and Pb. Furthermore, the alkali-metal ion exchange of K4Ge9 with LiCl in en results also in the oxidation of [Ge9]4- to [Ge9-Ge9]6- dimers which were isolated as partially and fully ion-exchanged salts such as K2[Li(en)2]4[Ge9-Ge9]  and [Li(en)2]6.5[Ge9-Ge9], respectively. NMR spectroscopic investigations of solutions of [Sn9]4- that contain variable Li: K ratio reveal  contact  K+/[Sn9]4-  ion pairs, while Li+/[Sn9]4-  form solvent-separated ion pairs. The role of Li ions on the solubility of Zintl phases and Li assisted oxidation of Zintl ions is highlighted.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500592"},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707846","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}
引用次数: 0
Chemoenzymatic Total Synthesis of Lansai B.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-25 DOI: 10.1002/chem.202500740
Marcel Schatton, Mona Haase, Julia Tenhaef, Catharina Gronkowsky, Stephan Noack, Joerg Pietruszka
{"title":"Chemoenzymatic Total Synthesis of Lansai B.","authors":"Marcel Schatton, Mona Haase, Julia Tenhaef, Catharina Gronkowsky, Stephan Noack, Joerg Pietruszka","doi":"10.1002/chem.202500740","DOIUrl":"https://doi.org/10.1002/chem.202500740","url":null,"abstract":"<p><p>Lansai B is an indole alkaloid whose biosynthesis is not yet elucidated. However, utilizing nature's tools enabled the stereoselective formation of this unique framework, first by providing the substituted tryptophan as starting material and later in the scaffold-building step forming the pyrroloindole motif. For the latter the C3-methyltransferase from Streptomyces griseoviridis (SgMT) is employed for the diastereoselective methylation. Investigating the scope of enzyme proved that introducing a bromide in 5-position was ideal for the synthetic endeavor. With this, the stage was set for the synthesis of Lansai B introducing the prenyl-group late via a Suzuki coupling.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500740"},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699152","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}
引用次数: 0
Synthesis of β,β-Dinaphthyl Amino Acids: Towards Molecular Gearing in Peptides and Mini-Proteins.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-25 DOI: 10.1002/chem.202404465
Timo Zimmer, Sergei I Ivlev, Armin Geyer
{"title":"Synthesis of β,β-Dinaphthyl Amino Acids: Towards Molecular Gearing in Peptides and Mini-Proteins.","authors":"Timo Zimmer, Sergei I Ivlev, Armin Geyer","doi":"10.1002/chem.202404465","DOIUrl":"https://doi.org/10.1002/chem.202404465","url":null,"abstract":"<p><p>We report the synthesis of β,β-dinaphthyl amino acids by directed CH-activation and their subsequent utilization in peptides. The synthesis of aromatic β-branched amino acids is limited by sterical crowding for large aromatic ring systems. The amino acids are transformed into adequately protected building blocks for solid phase peptide synthesis by using our amide weakening strategy. Our aim was to study the interactions of the side chain aryl groups in solution and solid state. Based on quantitative analysis of 1H NMR reference nuclei, we investigate conformational equilibria and compare them to established gearing systems.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404465"},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699252","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}
引用次数: 0
TiNiSi-Type ALiAu (A = Ca, Sr, Ba, Eu, Yb) Compounds: Alternative Use of "Excess" Electrons.
IF 3.9 2区 化学
Chemistry - A European Journal Pub Date : 2025-03-25 DOI: 10.1002/chem.202500134
Peter Höhn, Daniel Menendez Créspo, Matej Bobnar, Primož Koželj, Mitja Krnel, Yurii Prots, Marcus Schmidt, Frank Wagner, Yuri Grin
{"title":"TiNiSi-Type ALiAu (A = Ca, Sr, Ba, Eu, Yb) Compounds: Alternative Use of \"Excess\" Electrons.","authors":"Peter Höhn, Daniel Menendez Créspo, Matej Bobnar, Primož Koželj, Mitja Krnel, Yurii Prots, Marcus Schmidt, Frank Wagner, Yuri Grin","doi":"10.1002/chem.202500134","DOIUrl":"https://doi.org/10.1002/chem.202500134","url":null,"abstract":"<p><p>New TiNiSi-type compounds ALiAu (A = Ca, Sr, Ba, Eu, Yb) were obtained in the form of mm-sized single crystals by high-temperature centrifugation-aided filtration (HTCAF) from lithium melt. They are the first examples of TiNiSi-type representatives containing Li and a transition metal. The metallic phases show paramagnetic (Ca) or diamagnetic (Sr, Ba, Yb) behavior or antiferromagnetic ordering below 19 K (Eu). A new structural description is based on a hexagonal close packing with A occupying all octahedral and Li occupying half of the tetrahedral voids in an ordered fashion. Chemical bonding analysis supports the structural description and reveals the formation of eight-atomic stella-quadrangula bonds pinned on the empty tetrahedral holes, a bonding picture known from elemental metals.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500134"},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699255","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}
引用次数: 0
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