ChemistryEuropePub Date : 2025-05-24DOI: 10.1002/ceur.202500068
Satish Bhausaheb Dawange, Rai-Shung Liu
{"title":"Ligand-Dependent Chemoselectivity in Gold-Catalyzed Reactions between Anthranils and Diynamides. Formation of Spiro Azacyclic Compounds versus 1-Imino-1H-Indene-3-Carboximidamides","authors":"Satish Bhausaheb Dawange, Rai-Shung Liu","doi":"10.1002/ceur.202500068","DOIUrl":"https://doi.org/10.1002/ceur.202500068","url":null,"abstract":"<p>Gold-catalyzed reactions between anthranils and diynamides have been investigated, and their reaction chemoselectivity relies on the types of gold catalysts. With the same anthranil/diynamide mixtures, the use of PPh<sub>3</sub>AuCl/AgNTf<sub>2</sub> leads to formation of spiro azacyclic compounds, whereas P(<i>t</i>-Bu)<sub>2</sub>(<i>o</i>-biphenyl)AuCl/AgNTf<sub>2</sub> preferably yields 1-imino-1<i>H</i>-indene-3-carboximidamides instead. In the PPh<sub>3</sub>AuCl/AgNTf<sub>2</sub> system, an indole intermediate at low temperature for X-ray diffraction study is isolated; this isolable indole species requires anthranil and gold catalyst for efficient formation of spiro azacyclic products. In the case of P(<i>t</i>-Bu)<sub>2</sub>(<i>o</i>-biphenyl)AuCl/AgNTf<sub>2</sub>, the mechanism of its resulting 1-imino-1<i>H</i>-indene-3-carboximidamides is postulated based on literature reports.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500068","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635650","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 : 2025-05-23DOI: 10.1002/ceur.202500081
Lena Albers, Marc Schmidtmann, Thomas Müller
{"title":"Exploring the Reactivity of Germole Dianions with Aluminum Trichloride: Uncovering Versatile Pathways","authors":"Lena Albers, Marc Schmidtmann, Thomas Müller","doi":"10.1002/ceur.202500081","DOIUrl":"https://doi.org/10.1002/ceur.202500081","url":null,"abstract":"<p>The reactivity analysis of dipotassiumgermoldiides K<sub>2</sub><b>[1]</b> with aluminum trichloride in the presence of donors uncovers an unexpectedly broad range of products. The specific product formed varies, based on the donor's characteristics, its size, and the stoichiometric ratio between the donor and the aluminium trichloride. This leads to the formation of various products, including alumole complexes of germanium <b>3(Do)</b> (with Do = OEt<sub>2</sub>, <sup><i>i</i>Pr2Me2</sup>Im), cationic germole complexes of aluminylenes [<b>14</b>]<sup>+</sup>, and 2<i>H</i>-germole derivatives such as <b>15a</b>. The alumole complexes of germanium <b>3</b> are structurally best described as <i>nido</i>-type clusters or aluminagerma[5]pyramidanes. They show significant Lewis acidity and can be isolated only in the form of their donor complexes <b>3</b>(<b>Do</b>). The 2<i>H</i>-germole derivative <b>15a</b> promises a high synthetic potential due to its unprecedented germenide (R<sub>2</sub>C = Ge(:)-R) group group, which is part of a butadiene system and substituted with a reactive C–Al functionality.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500081","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635619","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 : 2025-05-15DOI: 10.1002/ceur.202580302
Dennis Reinhard, Sven M. Elbert, Wen-Shan Zhang, Frank Rominger, Rasmus R. Schröder, Michael Mastalerz
{"title":"Dead Ends and Detours Towards a Rigid Hexasalicylic Aldehyde Precursor for Triptycene-Based Porous Materials","authors":"Dennis Reinhard, Sven M. Elbert, Wen-Shan Zhang, Frank Rominger, Rasmus R. Schröder, Michael Mastalerz","doi":"10.1002/ceur.202580302","DOIUrl":"https://doi.org/10.1002/ceur.202580302","url":null,"abstract":"<p><b>The Cover Feature</b> illustrates the response of a butterfly-shaped V2Dy2 coordination cluster complex to microwave radiation in an external magnetic field. In their Research Article (DOI: 202500011), J. Arneth, J. Braun, A. K. Powell, R. Klingeler and co-workers from groups in Heidelberg and Karlsruhe report a new family of butterfly complexes that extend the existing library of butterflies towards using VIII ions. A systematic investigation of the nature of magnetic coupling using combined magnetisation and multifrequency high-field EPR studies revealed a strong interplay of single ion anisotropy and 3d-4f exchange.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202580302","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949840","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 : 2025-05-15DOI: 10.1002/ceur.202580301
Dr. Boram Park, Dr. Iwona Nierengarten, Dr. Jean-François Nierengarten
{"title":"Mechanochemical Synthesis of Pillar[5]arene-based [c2]Daisy Chain Rotaxanes","authors":"Dr. Boram Park, Dr. Iwona Nierengarten, Dr. Jean-François Nierengarten","doi":"10.1002/ceur.202580301","DOIUrl":"https://doi.org/10.1002/ceur.202580301","url":null,"abstract":"<p><b>The Front Cover</b>illustrates the solvent-free mechanochemical conditions used to functionalize daisy-chain assemblies. In their Research Article (DOI: 2500002), J.-F. Nierengarten and co-workers reveal the potential of mechanochemical conditions for the synthesis of pillar[5]arene-based mechanically interlocked nanostructures. Concentration effects are clearly beneficial when the reactions are performed under solvent-free conditions as daisy-chain assemblies are effectively present in the solid state despite the very weak tendency of the monomer to aggregate in solution. In other words, stoppered cyclic daisy-chain dimers that cannot be obtained in solution are now accessible.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202580301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143949839","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 : 2025-05-15DOI: 10.1002/ceur.202580303
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.202580303","DOIUrl":"https://doi.org/10.1002/ceur.202580303","url":null,"abstract":"<p><b>The Cover Feature</b> shows a parallel-stranded DNA duplex with a terminally attached luminescent lanthanoid complex, represented by a magic wand that lights up when the corresponding spell is cast. The glowing magic wand is waved around an emission spectrum of the complex, with an enchanted castle in the background. The duplex figure was generated from PDB entry 1JUU. More information can be found in the Research Article by J. Müller and co-workers (DOI: 202400116).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202580303","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143950251","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 : 2025-05-08DOI: 10.1002/ceur.202500047
Yikun Zhu, Ke Zheng, Zheng Wei, Yan Xia, Marina A. Petrukhina
{"title":"Probing Effects of Electron Addition to Polycyclic Conjugated Hydrocarbons Containing Four-Membered Rings","authors":"Yikun Zhu, Ke Zheng, Zheng Wei, Yan Xia, Marina A. Petrukhina","doi":"10.1002/ceur.202500047","DOIUrl":"https://doi.org/10.1002/ceur.202500047","url":null,"abstract":"<p>The rectangular cyclobutadiene (CBD, C<sub>4</sub>H<sub>4</sub>) is a unique moiety for building nonbenzenoid polycyclic conjugated hydrocarbons with interesting electron-accepting properties. Herein, the investigation on chemical reduction of several CBD-containing polycyclic hydrocarbons with increasing conjugation length is reported: biphenylene (C<sub>12</sub>H<sub>8</sub>), dimethyl[2]naphthalene (C<sub>22</sub>H<sub>16</sub>), and tetramethyl-dibenzo-[3]phenylene (C<sub>30</sub>H<sub>22</sub>). The two-step sequential reduction is first demonstrated by in situ spectroscopic investigation and then confirmed by the isolation of single crystals of the reduced products. The X-ray crystallographic analysis reveals the formation of several mono- and doubly reduced products in solvent-separated and complexed forms. The crystal structures for both neutral parents and corresponding reduced products unravel the changes in bond alternation in each ring of the fused systems. Density functional theory (DFT) and nucleus-independent chemical shift (NICS) scan calculations reveal that the two-electron addition reduces the aromatic character in the benzenoid rings but has minor influence on the antiaromatic CBD rings.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500047","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635363","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 : 2025-05-07DOI: 10.1002/ceur.202500049
Stefan Richter, Dušan Dimić, Peter Lönnecke, Goran N. Kaluđerović, Evamarie Hey-Hawkins
{"title":"Comparative Study of Platinum(II) and Platinum(IV) Complexes with 2-(Pyridin-2-ylmethylamino)acetic Acid and 4-(Pyridin-2-ylmethylamino)benzoic Acid: Experimental and Theoretical Analysis","authors":"Stefan Richter, Dušan Dimić, Peter Lönnecke, Goran N. Kaluđerović, Evamarie Hey-Hawkins","doi":"10.1002/ceur.202500049","DOIUrl":"https://doi.org/10.1002/ceur.202500049","url":null,"abstract":"<p>The coordination behavior of 2-(2-pyridin-2-ylmethylamino)acetic acid (<b>HL1</b>) and 4-(2-pyridin-2-ylmethylamino)benzoic acid (<b>HL2</b>) toward Pt<sup>II</sup> and Pt<sup>IV</sup> is investigated. While the corresponding carboxylato complexes are obtained with <b>HL1</b> (N,N,O coordination of <b>L1</b><sup><b>−</b></sup>, elimination of HCl; <b>1a</b> and <b>1b</b>), only N,N coordination of <b>HL2</b> which still features the carboxylic acid group is observed (<b>2a</b> and <b>2b</b>). Thus, complexes <b>2a</b> and <b>2b</b> would be suitable for subsequent conjugation to biomolecules using the free COOH group. On heating in air, the ligand in <b>2a</b> is oxidized (formal elimination of dihydrogen) to give the imine complex <b>3a</b>, which could also be obtained directly from the corresponding ligand <b>HL3</b> ((<i>Z</i>)-4-(pyridin-2-ylmethyleneamino)benzoic acid). The obtained complexes are characterized by <sup>1</sup>H, <sup>13</sup>C{<sup>1</sup>H} NMR and IR spectroscopy, elemental analysis, and, in the case of complexes <b>1a</b>, <b>1b</b>, and <b>3a</b>, also by single-crystal X-ray crystallography. In addition, quantum chemical calculations are carried out to gain deeper insights into the molecular structures and properties of both the complexes and their precursor ligands. A comparative study showed that the theoretical calculations are in good agreement with the experimental findings. This combined experimental and theoretical approach facilitated a comprehensive understanding of the coordination behavior and structural features of the investigated complexes.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500049","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635192","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 : 2025-05-06DOI: 10.1002/ceur.202500013
Fiammetta Vitulano, Andrea Solida, Letizia Sorti, Carlo F. Morelli, Alessandro Minguzzi, Alberto Vertova
{"title":"Alcohol and Carbonyl Redox Reactions in Electrochemical Organic Synthesis","authors":"Fiammetta Vitulano, Andrea Solida, Letizia Sorti, Carlo F. Morelli, Alessandro Minguzzi, Alberto Vertova","doi":"10.1002/ceur.202500013","DOIUrl":"https://doi.org/10.1002/ceur.202500013","url":null,"abstract":"<p>The primary aim of this review is to provide an overview of relevant and efficient methods in organic electrosynthesis, presented in a reader-friendly format. The focus is on the electrochemical oxidation of primary alcohols to aldehydes and carboxylic acids, the oxidation of aldehydes to carboxylic acids, and the oxidation of secondary alcohols to ketones. Additionally, the corresponding electrochemical reductions, such as the reduction of carboxylic acids to aldehydes and primary alcohols, the reduction of aldehydes to primary alcohols, and the reduction of ketones to secondary alcohols, are also covered. For each type of reaction, an easy-to-follow table provides readers with essential information (e.g., substrates, working electrode, electrolyte, cell type, synthesis notes, and references), enabling a quick yet comprehensive overview of the electrosynthetic possibilities for a given functional group. The review also explores recent advancements in organic electrosynthesis, encompassing both direct and mediated techniques. As electrochemical alternatives to classical organic synthesis continue to garner increasing attention, it is hoped that this review will serve as a valuable resource for those interested in evaluating these synthetic approaches.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635011","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 : 2025-05-06DOI: 10.1002/ceur.202500041
Floriane Doche, Thibault Gallavardin, Thomas Poisson, Tatiana Besset
{"title":"Energy Transfer Catalysis Enabled 2,2,2-Trifluoroethoxy-Amination of Olefins","authors":"Floriane Doche, Thibault Gallavardin, Thomas Poisson, Tatiana Besset","doi":"10.1002/ceur.202500041","DOIUrl":"https://doi.org/10.1002/ceur.202500041","url":null,"abstract":"<p>A thioxanthone-catalyzed 2,2,2-trifluoroethoxyamination of olefins is developed <i>via</i> the formation of the corresponding alkoxy and iminyl radicals using unprecedented, easily prepared, and bench-stable oxime ethers as bifunctional reagents. To bypass possible side reactions (1,2-Hydrogen Atom Transfer (HAT), H-abstraction, and β-scission), the high reactivity of the alkoxy radical is fine-tuned to promote the selective and challenging formation of a C<span></span>OCH<sub>2</sub>CF<sub>3</sub> bond. This reaction, involving a triplet energy transfer process, allows the concomitant formation of a C<span></span>N and C<span></span>OAlk bond, so far uncharted, using bifunctional oxime ether reagents. Hence, the difunctionalization of a myriad of electron-rich alkenes selectively afforded the anti-Markovnikov products with a large functional group tolerance (44 examples, up to 77% yield), offering a straightforward and complementary regioselectivity compared to the existing approaches for the difunctionalization of alkenes with 2,2,2-trifluoroethanol. Post-functionalization reactions and mechanistic investigations provided key insights into the reaction mechanism of this transformation.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635009","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 : 2025-04-30DOI: 10.1002/ceur.202500067
Joseph El Khoury, Thibault Thierry, Yannick Geiger, Stéphane Bellemin-Laponnaz
{"title":"Autoinductive Effects in Zinc-Catalyzed Alkylations of Benzaldehyde Mediated by Simple Chiral β-Amino Alcohol Ligands","authors":"Joseph El Khoury, Thibault Thierry, Yannick Geiger, Stéphane Bellemin-Laponnaz","doi":"10.1002/ceur.202500067","DOIUrl":"https://doi.org/10.1002/ceur.202500067","url":null,"abstract":"<p>The first report on enantioselective zinc-catalyzed aldehyde alkylation mediated by a chiral auxiliary has been revisited in the context of recent advances in the field. The enantioselectivity of the alcohol formed as a function of the progress of the reaction has been studied with four different amino alcohols. During the course of the reaction, the enantiomeric ratio, in which the product is formed, is inverted, giving rise to enantiodivergence, a phenomenon that is also dependent on the catalyst loading. By combining these results with studies on nonlinear effects as well as other mechanistic studies, a model that accounts for the enantiodivergence is derived. It turns out that it is a case of catalytic autoinduction in which an active species with better enantioselectivity than the native catalyst is generated.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500067","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635668","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}