ChemistryEuropePub Date : 2025-03-12DOI: 10.1002/ceur.202500044
Max Deering, Malcolm George, Prof. Craig P. Butts, Prof. Varinder K. Aggarwal
{"title":"A Simple NMR-Based Rule for Stereochemical Assignment of 1,5-Diols in Polyketides","authors":"Max Deering, Malcolm George, Prof. Craig P. Butts, Prof. Varinder K. Aggarwal","doi":"10.1002/ceur.202500044","DOIUrl":"https://doi.org/10.1002/ceur.202500044","url":null,"abstract":"<p>Polyketide natural products are a valuable source of inspiration for therapeutic lead compounds, but their diversity and complexity make structure elucidation highly challenging. Here, we report a comprehensive analysis of the relative stereochemical assignment of 1,5-diol moieties in polyketides – a very common but challenging structural element to elucidate. We have found that the chemical shift difference (Δδ<sub>HaHb</sub>) between the diastereotopic central methylene protons is >0.17 ppm for <i>syn</i> isomers and <0.13 for <i>anti</i> isomers. This simple rule has been shown to correctly predict the relative 1,5-diol stereochemistries in over 40 natural products, except those cases where the flanking substituents have a large steric difference (tertiary vs primary alkyl) or are constrained within conformationally restricted rings. These resulting Δδ<sub>HaHb</sub> rules have then been used to predict the relative configuration of several previously unassigned natural products, enabling facile, non-destructive structure elucidation.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500044","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-03-10DOI: 10.1002/ceur.202580202
Alexander A. Fadeev, Martin Kotora
{"title":"Cover Feature: Anticipating Natural Phenolics Through Visible Light-Induced Photorearrangement of Quinones (ChemistryEurope 2/2025)","authors":"Alexander A. Fadeev, Martin Kotora","doi":"10.1002/ceur.202580202","DOIUrl":"https://doi.org/10.1002/ceur.202580202","url":null,"abstract":"<p><b>The Cover Feature</b> represents the smooth intramolecular photoisomerization of quinones into diverse phenolic compounds in solution under exposure to blue light, which is represented by a “blue moon”. Given that many quinones co-occur in nature with hydroquinones and other hydroxyarenes, such a transformation allows us to anticipate the presence of these substances in natural sources through a light-induced synthesis. More information can be found in the Research Article by A. A. Fadeev and M. Kotora (DOI: 10.1002/ceur.202400094).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202580202","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581800","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-03-10DOI: 10.1002/ceur.202580201
Dr. Aaron Torres-Huerta, Dr. Karolis Norvaisa, Dr. Alessio Cataldo, Pierre-Olivier Tits, Priyanka Rani Panda, Dr. Christopher M. Dias, Prof. Dr. Anthony P. Davis, Dr. Samantha E. Bodman, Dr. Stephen J. Butler, Dr. Hennie Valkenier
{"title":"Front Cover: Structural Requirements of Synthetic Anionophores for Inorganic Phosphate and Phosphate Esters (ChemistryEurope 2/2025)","authors":"Dr. Aaron Torres-Huerta, Dr. Karolis Norvaisa, Dr. Alessio Cataldo, Pierre-Olivier Tits, Priyanka Rani Panda, Dr. Christopher M. Dias, Prof. Dr. Anthony P. Davis, Dr. Samantha E. Bodman, Dr. Stephen J. Butler, Dr. Hennie Valkenier","doi":"10.1002/ceur.202580201","DOIUrl":"https://doi.org/10.1002/ceur.202580201","url":null,"abstract":"<p><b>The Front Cover</b> shows liposomes with synthetic anion receptors embedded in their membrane and different phosphate species to be transported. In their Research Article (DOI: 10.1002/ceur.202400076), H. Valkenier and co-workers show that phosphate diesters are readily transported across lipid bilayers, followed by phosphate monoesters, whereas inorganic phosphate is the most difficult to transport and requires the effective encapsulation by an anion receptor. Artwork by A. Torres-Huerta.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202580201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-03-05DOI: 10.1002/ceur.202400118
Aleksandar Kondinski
{"title":"Digital Metallo-Supramolecular Chemistry","authors":"Aleksandar Kondinski","doi":"10.1002/ceur.202400118","DOIUrl":"https://doi.org/10.1002/ceur.202400118","url":null,"abstract":"<p>Metal-organic cages (MOCs) are supramolecular assemblies designed through complex chemical and spatial reasoning. While chemical creativity and modelling have advanced greatly the engineering of new and functional MOCs, their synthesis and characterisation have remained labour-intensive. Recently, the Cooper group developed a self-driving laboratory system that automates the synthesis and characterisation of MOCs, their building units and host-guest derivatives, through benchtop instrumentation, robotics, and heuristic decision-making. The overall system provides a critical step towards the merging of digital and supramolecular chemistry.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400118","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-02-09DOI: 10.1002/ceur.202400093
Maciej Piejko, Javier E. Alfonso-Ramos, Joseph Moran, Thijs Stuyver
{"title":"Abiotic Ribonucleoside Formation in Aqueous Microdroplets: Mechanistic Exploration, Acidity, and Electric Field Effects","authors":"Maciej Piejko, Javier E. Alfonso-Ramos, Joseph Moran, Thijs Stuyver","doi":"10.1002/ceur.202400093","DOIUrl":"https://doi.org/10.1002/ceur.202400093","url":null,"abstract":"<p>Aqueous microdroplets have been reported to dramatically increase the rate of chemical reactions. Proposed mechanisms for this acceleration include confinement effects upon droplet evaporation, and Brønsted acid or electric field catalysis at the air-water interface. However, computational investigations indicate that the operation of these mechanisms is reaction-dependent, with conclusive evidence for a role for electric field catalysis still lacking. Here, we present a computational investigation of the reported abiotic phosphorylation of ribose and the subsequent formation of ribonucleosides, focusing on acidity and oriented external electric field (OEEF) effects. The most plausible reaction mechanism identified involves the protonation of ribose, followed by carbocation formation and an S<sub><i>N</i></sub>2 substitution step. Without an OEEF, all considered pathways are thermally inaccessible. However, in the presence of a significant OEEF, the S<sub><i>N</i></sub>2-based pathway, leading to the <i>β</i>-ribonucleoside isomer, becomes highly stabilized, reducing the energetic span to a thermally accessible 12–13 kcal/mol. Surprisingly, the OEEF-mediated reaction closely mirrors the enzymatic mechanism of phosphorolysis via S<sub><i>N</i></sub>2 substitution, including a pronounced anomeric selectivity. Our results support the hypothesis that some reactions in aqueous microdroplets are accelerated by electric fields and provide further evidence for the importance of electrostatic catalysis in biological systems, particularly for phosphorylase enzymes.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400093","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581357","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-02-07DOI: 10.1002/ceur.202400105
Ren-Rui Xu, Chang-Sheng Kuai, Prof. Dr. Xiao-Feng Wu
{"title":"Palladium-Catalyzed Selectivity Controlled Highly Efficient Carbonylative Synthesis of Isoquinoline-1,3(2H,4H)-diones and Indanones","authors":"Ren-Rui Xu, Chang-Sheng Kuai, Prof. Dr. Xiao-Feng Wu","doi":"10.1002/ceur.202400105","DOIUrl":"https://doi.org/10.1002/ceur.202400105","url":null,"abstract":"<p>Compared to the methods that rely on complex and structurally unique substrates for the synthesis of heterocyclic compounds through intra- and intermolecular cyclization, strategies starting from simple and readily available substrates, combined with finely tuned catalytic system to achieve different chemoselectivity, offer significant advantages in terms of efficiency, cost-effectiveness, and versatility. Herein, we present a palladium-catalyzed carbonylation strategy that enables the selective and efficient synthesis of isoquinoline-1,3(2<i>H</i>,4<i>H</i>)-dione and indanone derivatives via distinct reaction pathways. Notably, the chemoselectivity was not determined by the differences in reactivity at the reaction sites but instead arises from the generation of distinct active palladium species under nearly identical reaction conditions, which subsequently react on the same reaction site but lead to different products.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400105","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-02-03DOI: 10.1002/ceur.202400094
Alexander A. Fadeev, Martin Kotora
{"title":"Anticipating Natural Phenolics Through Visible Light-Induced Photorearrangement of Quinones","authors":"Alexander A. Fadeev, Martin Kotora","doi":"10.1002/ceur.202400094","DOIUrl":"https://doi.org/10.1002/ceur.202400094","url":null,"abstract":"<p>A general protocol for the photorearrangement of substituted benzo- and naphthoquinones using monochromatic blue light irradiation in solution was developed. During this process, the quinone ring is transformed into the hydroquinone, while the substituent undergoes desaturation or annulation onto the proximal oxygen of the formed hydroquinone. We found that desaturation was preferred for acyclic saturated substituents, such as alkyl groups, and the tendency for annulation was observed for both cyclic and acyclic unsaturated substituents (allyl, alkenyl, aryl). The diversity of the participating substituents and the functional group tolerance of this transformation allowed us to prepare 10 natural phenolic compounds, suggesting that visible light may likewise induce their formation from the respective quinones in natural sources.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400094","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-02-03DOI: 10.1002/ceur.202400116
Carla Bardehle, Marian Hebenbrock, Alexander Hepp, Jens Müller
{"title":"Lumos: A β-Diketone-Derived Artificial Nucleobase Forming Inter-Strand Complexes in DNA that Promote Lanthanoid Ion Luminescence","authors":"Carla Bardehle, Marian Hebenbrock, Alexander Hepp, Jens Müller","doi":"10.1002/ceur.202400116","DOIUrl":"https://doi.org/10.1002/ceur.202400116","url":null,"abstract":"<p>A novel artificial nucleobase, 1-(3-(hydroxymethyl)phenyl)-3-phenylpropane-1,3-dione (Hdbm<sup>OR</sup>), containing a <i>β</i>-diketone designed to form inter-strand complexes that resemble metal-mediated base pairs, was synthesized and characterized towards its lanthanoid ion binding properties. Based on UV/vis spectra, a (labile) coordination of Eu<sup>III</sup> and Sm<sup>III</sup> by the benzyl-functionalized model ligand is proposed, allowing the detection of distinct luminescence patterns upon coordination under alkaline conditions. The compatibility of the nucleoside analog with automated solid-phase DNA synthesis was proven by the generation of a dinucleotide. NMR spectroscopic characterization of this dinucleotide revealed a temperature-dependent equilibrium of two conformers, which likely involve hydrogen bonding of the <i>β</i>-diketone moiety and the deoxyribose and/or phosphate moieties. The antenna effect of the new ligand promoting the luminescence of Eu<sup>III</sup> is retained upon incorporation into DNA. Modification of a parallel-stranded DNA duplex with a terminal homo base pair of Hdbm<sup>OR</sup> allows, despite natural fraying of DNA, a thermal stabilization of about 3 °C upon coordination of Eu<sup>III</sup> or Sm<sup>III</sup>. Temperature-dependent luminescence spectroscopy demonstrates a direct correlation between the thermal stability of the duplex and its luminescence intensity. The ligand extends the library of artificial nucleobases for lanthanoid-mediated base pairs, combining the luminescence properties of lanthanoid complexes with the self-assembly properties of DNA.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400116","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-02-03DOI: 10.1002/ceur.202400076
Dr. Aaron Torres-Huerta, Dr. Karolis Norvaisa, Dr. Alessio Cataldo, Pierre-Olivier Tits, Priyanka Rani Panda, Dr. Christopher M. Dias, Prof. Dr. Anthony P. Davis, Dr. Samantha E. Bodman, Dr. Stephen J. Butler, Dr. Hennie Valkenier
{"title":"Structural Requirements of Synthetic Anionophores for Inorganic Phosphate and Phosphate Esters","authors":"Dr. Aaron Torres-Huerta, Dr. Karolis Norvaisa, Dr. Alessio Cataldo, Pierre-Olivier Tits, Priyanka Rani Panda, Dr. Christopher M. Dias, Prof. Dr. Anthony P. Davis, Dr. Samantha E. Bodman, Dr. Stephen J. Butler, Dr. Hennie Valkenier","doi":"10.1002/ceur.202400076","DOIUrl":"https://doi.org/10.1002/ceur.202400076","url":null,"abstract":"<p>The transmembrane transport of anions is a promising application of synthetic anion receptors. Numerous anionophores have been developed for chloride over the past decades. Despite the biological relevance of phosphate and phosphate esters, very few reports on their transport by synthetic systems exist. Here we report a systematic study on the transport of diphenyl phosphate, phenyl phosphate, and inorganic phosphate by five different anionophores. The transport of these phosphates into liposomes was monitored by fluorescence spectroscopy, <sup>31</sup>P NMR spectroscopy, and an ion selective electrode. The results of these experiments showed that diphenyl phosphate is readily transported by most chloride ionophores. The transport of phenyl phosphate is more challenging but can be enhanced by better shielding of the phosphate group. Inorganic phosphate is the most challenging to transport and this was achieved using a macrocyclic anionophore with eight preorganised H-bond donors. These results pave the way for the development of anionophores for inorganic phosphate as well as phosphate esters.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400076","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemistryEuropePub Date : 2025-02-03DOI: 10.1002/ceur.202400092
Qikun Wu, Prof. Dr. Kei Muto, Prof. Dr. Junichiro Yamaguchi
{"title":"An Umpolung Approach for C2-Selective C−H Amination of Azines by Palladium Catalysis","authors":"Qikun Wu, Prof. Dr. Kei Muto, Prof. Dr. Junichiro Yamaguchi","doi":"10.1002/ceur.202400092","DOIUrl":"https://doi.org/10.1002/ceur.202400092","url":null,"abstract":"<p>The site-selective C−H amination of azines is a critical challenge due to the broad applications of amino azines in biologically important compounds. In this work, we report a conceptually novel approach to the electrophilic C2-selective C−H amination of azines using <i>O</i>-benzoylhydroxylamines, catalyzed by a benzyl–palladium complex. A key feature of this transformation is the formation of the distal C−N bond via a benzyl–Pd intermediate, facilitated by a malonate substituent on the azine as a remote directing group. This strategy effectively overrides the inherent polarity mismatch typically observed in electrophilic C2-C−H aminations. The reaction exhibits high site-selectivity and demonstrates towards amine-sensitive functional group, highlighting its synthetic utility.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400092","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143581480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}