Yongxing Wang, Rogelio Gomez Pineiro, Rébecca Leblay, Michel Giorgi, Sylvain Bertaina, Maylis Orio, Bruno Faure, Marius Réglier, A Jalila Simaan
{"title":"OXIDATION-DEFORMYLATION CASCADE CATALYZED BY A MONONUCLEAR COPPER COMPLEX.","authors":"Yongxing Wang, Rogelio Gomez Pineiro, Rébecca Leblay, Michel Giorgi, Sylvain Bertaina, Maylis Orio, Bruno Faure, Marius Réglier, A Jalila Simaan","doi":"10.1002/chem.202500626","DOIUrl":"https://doi.org/10.1002/chem.202500626","url":null,"abstract":"<p><p>In this study, two copper complexes were synthesized using N3 (arising from two pyridines and one amide group) containing ligands N-(2-picolyl)picolinamide (L1H) and bis(2-pyridylcarbonyl)amine (L2H), forming [(L1)CuII(OH2)(NO3)] (1) and [(L2)CuII(OH2)2](NO3) (2). The reaction of complex 1 with hydrogen peroxide in alcoholic solvents yielded a formate-bound complex. Studies with isotopically labeled 13C ethanol indicated that formate originates from the C1 of ethanol after C-C bond cleavage. Complex 1 was found to catalytically convert primary alcohols into formic acid probably following a two-step process: (i) alcohol oxidation to aldehyde and (ii) aldehyde deformylation. Further experiments with 2-phenylpropionaldehyde (2-PPA) confirm the ability of complex 1 to catalyze aldehyde deformylation. Both steps of the reaction are associated with significant kinetic deuterium isotope effects (KDIE), suggesting that hydrogen atom abstractions (HAA) occur during the rate-determining steps of both conversions. Overall, this system proposes a clean catalytic process for alcohol-to-formic acid conversion, operating under mild conditions, and offering potential synthetic applications.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500626"},"PeriodicalIF":3.9,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466356","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}
Chuanshuai Li, Yong Li, Yusen Luo, Klaudia Michaliszyn, Iria Bolano Losada, Md Kamal Hossain, Fatma Elantabli, Meiyuan Guo, Lintang Hizbullah, Derek A Tocher, Matti Haukka, Petter Persson, Julio Lloret-Fillol, Benjamin Dietzek-Ivanšić, Ebbe Nordlander
{"title":"Photoinduced hydrogen evolution catalyzed by Co(II) complexes of N5-donor ligands.","authors":"Chuanshuai Li, Yong Li, Yusen Luo, Klaudia Michaliszyn, Iria Bolano Losada, Md Kamal Hossain, Fatma Elantabli, Meiyuan Guo, Lintang Hizbullah, Derek A Tocher, Matti Haukka, Petter Persson, Julio Lloret-Fillol, Benjamin Dietzek-Ivanšić, Ebbe Nordlander","doi":"10.1002/chem.202404499","DOIUrl":"https://doi.org/10.1002/chem.202404499","url":null,"abstract":"<p><p>Three new cobalt complexes of the general formula [Co(II)(L)(CH3CN) ]2+, where L is one of three pentadentate nitrogen-donor ligands based on the N4Py framework, have been synthesized and characterized. The capacity of the three complexes to effect photocatalytic proton reduction has been examined. Their photocatalytic activities in the presence of [Ru(bpy)3]2+, acting as a photosensitizer, and ascorbic acid, acting as a sacrificial electron donor, were screened in a water/acetonitrile mixture. The photochemical mechanism, as revealed by nanosecond time-resolved transient absorption spectroscopy, involves reaction of the excited sensitizer with ascorbic acid to yield [Ru(bpy)3]+ as a primary photogenerated reductant, capable of electron transfer to the cobalt catalyst(s). Under the experimental conditions used, partial decomposition of both the sensitizer and the catalyst is the main deactivation channel for photocatalysis. Optimization of reaction conditions indicated that the use of more reducing iridium or copper-based photosensitizers had a beneficial effect on the catalytic performance. The effect of the different ligands on the catalytic activities of the corresponding cobalt complexes have been investigated by DFT calculations.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404499"},"PeriodicalIF":3.9,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466361","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}
Ya Fang, Wei Ma, Zhaobo Zhou, Xuanjia Wang, Xi Chen, Jiaxiang Wang, Xiaolei Wang
{"title":"Convenient Synthesis of β-C-acyl Glycosides and its Application in the Synthesis of Scleropentaside A, Scleropentaside B and the Derivatives of Dapagliflozin.","authors":"Ya Fang, Wei Ma, Zhaobo Zhou, Xuanjia Wang, Xi Chen, Jiaxiang Wang, Xiaolei Wang","doi":"10.1002/chem.202500044","DOIUrl":"https://doi.org/10.1002/chem.202500044","url":null,"abstract":"<p><p>C-Glycosides are a common feature in numerous bioactive natural compounds and play a crucial role as mimics of O/N-glycosides. Our process for synthesizing β-C-acyl glycosides involves a reductive cross-coupling of protected glycosyl bromides with the corresponding carboxylic acid, followed by base-assisted deprotection and isomerization. This method is compatible with diverse glycosyl donors, including disaccharides. Consequently, we achieved the total synthesis of the natural products scleropentaside A and scleropentaside B with exceptional efficiency. These β-C-acyl glycosides can be readily transformed into novel forms of C-glycosides capable of disrupting signaling pathways linked to various pathological conditions, such as diabetes.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500044"},"PeriodicalIF":3.9,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466350","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}
Márton Bircher, Konstantin Karaghiosoff, Mátyás Czugler, Angéla Takács, László Kőhidai, László Drahos, György Keglevich
{"title":"New Cytotoxic Derivatives by the Phosphorylation and Phosphinoylation of Diethyl α-Amino-α-Aryl-methylphosphonates.","authors":"Márton Bircher, Konstantin Karaghiosoff, Mátyás Czugler, Angéla Takács, László Kőhidai, László Drahos, György Keglevich","doi":"10.1002/chem.202500370","DOIUrl":"https://doi.org/10.1002/chem.202500370","url":null,"abstract":"<p><p>In order to make available new derivatives, diethyl α-amino-α-aryl-methylphosphonates were subjected to phosphorylation, phosphinoylation and even thiophosphinoylation by reaction with phosphoryl chlorides, diphenylphosphinoyl chloride, and with the mixture of diphenylchlorophosphine and elemental sulfur, respectively. The X-ray crystal structures of the diphenylphosphinoyl and the diphenylthiophosphinoyl derivatives revealed molecular and supramolecular similarities, as well as a few differences too. An essential conformation change, along with packing differences are attributable to a change of one heteroatom: an oxygen for a sulfur in one of the P=X function. The diethyl diethylphosphoryl-aminobenzylphosphonates showed the highest antiproliferative effects on multiple myeloma cells, while the thiophosphinoylated diethyl aminobenzylphosphonate was the most effective on pancreatic ductal adenocarcinoma cells.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500370"},"PeriodicalIF":3.9,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466354","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}
Stephen Franzese, Chaoyu Ren, Wallace Wing Ho Wong
{"title":"Base-Induced Apparent Inverted Solvatochromism in Pyridinium Phenolates.","authors":"Stephen Franzese, Chaoyu Ren, Wallace Wing Ho Wong","doi":"10.1002/chem.202404678","DOIUrl":"https://doi.org/10.1002/chem.202404678","url":null,"abstract":"<p><p>Due to conflicting reports regarding the solvatochromism of p-extended pyridinium-phenolate dyes, the choice of base (N,N,N',N'-tetramethylguanidine or 1M tetrabutylammonium hydroxide in methanol) used to deprotonate the dyes was investigated. Three known dyes were synthesized and their UV-vis absorbance spectra were measured in a range of solvent using the two bases and the zwitterionic forms of the dyes. It was found that the methanolic tetrabutylammonium hydroxide could cause the appearance of inverted solvatochromism in negatively solvatochromic dyes when used in solvents of sufficiently low polarity. This was attributed to the presence of the polar, hydrogen bond donating methanol which preferentially solvates the dye, increasing the polarity it observes. Informed by these results, recommendations are presented for the methods used to compare solvatochromic dyes.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404678"},"PeriodicalIF":3.9,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466692","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}
Vit Kremlacek, Erik Kertesz, Milan Erben, Ales Ruzicka, Roman Jambor, Zoltan Benko, Libor Dostál
{"title":"OXIDATIVE ADDITION-REDUCTIVE ELIMINATION SUPPORTED BY A LIGAND-ELEMENT COOPERATION AT THE ARSINIDENE AND STIBINIDENE CENTER.","authors":"Vit Kremlacek, Erik Kertesz, Milan Erben, Ales Ruzicka, Roman Jambor, Zoltan Benko, Libor Dostál","doi":"10.1002/chem.202404751","DOIUrl":"https://doi.org/10.1002/chem.202404751","url":null,"abstract":"<p><p>The treatment of pnictinidenes [2-(RNHCH2)-6-(RN=CH)C6H3]E (1As/Sb) (where E = As or Sb) with benzoyl peroxide provided compounds [2-(DippNCH2)-6-(DippN=CH)C6H3]E(O2CPh) (2As/Sb) as a result of two step procedure, i.e. oxidation of the pnictogen centre followed by the elimination of benzoic acid. The reaction between 1As and diphenyl disulfide proceeded in the same vein yielding thiophenol and [2-(DippNCH2)-6-(DippN=CH)C6H3]As(SPh) (3As). Analogous reaction of 1Sb furnished a mixture of [2-(DippNHCH2)-6-(DippN=CH)C6H3]Sb(SPh)2 (3´Sb), [2-(DippNCH2)-6-(DippN=CH)C6H3]Sb(SPh) (3Sb) and PhSH, while NMR studies proved the existence of a dynamic equilibrium between all three compounds in solution and removal of incipient PhSH was necessary for the isolation of 3Sb. Both 1As/Sb smoothly reacted with 2-nitrosotoluene leading to [2-(DippNCH2)-6-(DippN=CH)C6H3]E(O-NH-2-Me-Ph) 4As/Sb and with 4-phenyl-1,2,4-triazoline-3,5-dione giving [2-(DippNCH2)-6-(DippN=CH)C6H3]E[(N(CO)-NH(CO))N-Ph] 5As/Sb. All compounds were characterized by IR, Raman, NMR spectroscopy, and the molecular structures, except for 3As and 5Sb, were determined by single-crystal X-ray diffraction. Furthermore, we scrutinized the thermally induced reductive elimination of benzoic acid and thiophenol from 2-3As/Sb, respectively, and that of 4-phenylurazole from 5As. These eliminations involve C-H activation at the CH2N group, and the recovery of the pnictinidene center in [2,6-(RN=CH)2C6H3]E (6As/Sb). Using DFT calculations a plausible mechanism was suggested for all investigated reactions, which are in good agreement with the experimental observations.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404751"},"PeriodicalIF":3.9,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466358","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}
Kenneth Wärnmark, Lisa H M de Groot, Clara García-Mateos, Catherine E Johnson, Valtýr Freyr Hlynsson, Alpesh K Sharma, Reiner Lomoth
{"title":"Base-Promoted Homolytic Aromatic Substitution (BHAS) Reactions and Hydrodehalogenations Driven by Green Light and an Iron(III)-NHC Photoredox Catalyst.","authors":"Kenneth Wärnmark, Lisa H M de Groot, Clara García-Mateos, Catherine E Johnson, Valtýr Freyr Hlynsson, Alpesh K Sharma, Reiner Lomoth","doi":"10.1002/chem.202500409","DOIUrl":"https://doi.org/10.1002/chem.202500409","url":null,"abstract":"<p><p>An Fe(III)-NHC complex has been employed for the green light driven catalysis of base-promoted homolytic aromatic substitution (BHAS) reactions. Tributylamine was used as a sacrificial electron donor, together with a potassium carbonate base in dimethyl sulfoxide as solvent. In contrast to previously studied photocatalysts, the excited Fe(III)-NHC complex is not reducing the arylhalide substrates. Instead, the latter are activated by α-aminoalkyl radicals formed upon reductive quenching of the photocatalyst by tributylamine. Avoiding strongly reducing photocatalysts as well as strong base, these mild reaction conditions allowed for the expansion of the substrate scope to accommodate also aldehyde and ester substituents. 100% conversion was obtained after 48 hrs of irradiation. In this way a wide variety of cyclized products and their corresponding hydrodehalogenated products were obtained as isolated and pure compounds, in the vast majority of cases.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202500409"},"PeriodicalIF":3.9,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466693","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}
Axel Steinbrueck, Matthew L. Reback, Christoph Rumancev, Daniel Siegmund, Jan Garrevoet, Gerald Falkenberg, Axel Rosenhahn, Aram Prokop, Nils Metzler-Nolte
{"title":"Cover Feature: Quinizarin Gold(I) N-Heterocyclic Carbene Complexes with Synergistic Activity Against Anthracycline-Resistant Leukaemia Cells: Synthesis and Biological Activity Studies (Chem. Eur. J. 11/2025)","authors":"Axel Steinbrueck, Matthew L. Reback, Christoph Rumancev, Daniel Siegmund, Jan Garrevoet, Gerald Falkenberg, Axel Rosenhahn, Aram Prokop, Nils Metzler-Nolte","doi":"10.1002/chem.202581104","DOIUrl":"https://doi.org/10.1002/chem.202581104","url":null,"abstract":"<p><b>The Cover Feature</b>, created by Aditi Mulik from the Ruhr-Universität Bochum, illustrates a cellular tug-of-war between the design goals for cancer therapeutics of prioritizing selective targeting or increased cytotoxicity. In the associated Research Article (DOI: 10.1002/chem.202404147), N. Metzler-Nolte and co-workers explain how mitochondrial targeting allowed the less-cytotoxic compound to overcome resistance mechanisms and re-sensitized cancer cells to treatment.\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 11","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581104","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446668","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":"The Lewis Acidity of Bare and Crown Ether-Complexed Germanium(II) and Tin(II) Cations.","authors":"Sarah McOnie, Andrew Henry, Kim Marie Baines","doi":"10.1002/chem.202404769","DOIUrl":"https://doi.org/10.1002/chem.202404769","url":null,"abstract":"<p><p>The Gutmann-Beckett and Fluoride Ion Affinity methods were used to assess the Lewis acidity of a variety of dicationic germanium(II) and tin(II) crown ether complexes and the corresponding neutral halides. The coordination of two or more equivalents of triethylphosphine oxide (TEPO) was observed which was accompanied by full or partial replacement of the crown ether or chloride ligands from the metal centre illustrating the importance of unambiguously identifying the species in solution to enable a meaningful discussion of relative Lewis acidities. From the coordination complexes observed, the germanium(II) centre was found, in general, to be more Lewis acidic than the tin(II) centre. The crown ether ligands, when retained, had little influence on the Lewis acidity of the complex and may, for ease of synthesis, be used as convenient precursors to \"bare\" Ge(II) and Sn(II) dicationic catalysts.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202404769"},"PeriodicalIF":3.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143466367","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}
Maciej P. Paprocki, Kasper K. Sørensen, Knud J. Jensen
{"title":"Front Cover: pH Controlled Transient Cyclization of Peptides for Increased Stability towards Oral Delivery (Chem. Eur. J. 11/2025)","authors":"Maciej P. Paprocki, Kasper K. Sørensen, Knud J. Jensen","doi":"10.1002/chem.202581101","DOIUrl":"https://doi.org/10.1002/chem.202581101","url":null,"abstract":"<p><b>The Front Cover</b> shows the pH-responsive linearization of cyclic peptides as a strategy for transient protection of peptides to extend their half-life in model systems. More information can be found in the Research Article by K. J. Jensen and co-workers (DOI: 10.1002/chem.202403503). Cover design by Niels Johan Christensen, PhD.\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 11","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202581101","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143446665","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}