{"title":"In Situ Generation of Alkyl–λ3–Iodanes as Soft and Highly Reactive Electrophiles","authors":"Rina Katsuta, Takayuki Watanabe, Keitaro Matsuoka, Keito Watanabe, Kosuke Higashida, Tatsuhiko Yoshino, Shigeki Matsunaga","doi":"10.1002/ceur.202500154","DOIUrl":"https://doi.org/10.1002/ceur.202500154","url":null,"abstract":"<p>Hypervalent iodine compounds have found various applications in organic chemistry and related research fields. Compared with aryl-, alkynyl-, and alkenyl-substituted iodanes and iodonium salts, alkyl–λ<sup>3</sup>–iodanes have been much less studied due to their infamous instability and the lack of convenient methods for their generation. Herein, it is reported that the reaction between a tetraalkylsilane and iodine tris(trifluoroacetate) at low temperature cleanly generates the corresponding alkyl–λ<sup>3</sup>–iodane in commonly used chlorinated solvents. The in situ-generated alkyl–λ<sup>3</sup>–iodanes are reasonably stable at low temperature, and Me–λ<sup>3</sup>–iodane serves as a soft and highly electrophilic methylating agent for tertiary sulfonamides. This alkylative activation of tertiary sulfonamides provides reactive sulfonyl ammonium intermediates that can achieve transamidation and fluorination reactions, thus demonstrating the synthetic utility of the in situ-generated alkyl–λ<sup>3</sup>–iodane.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128857","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 : 2025-07-06DOI: 10.1002/ceur.202500142
Chantsalmaa Berthold, Deniz F. Bekiş, Jan Moritz, Gilles Stebens, Burkhard Butschke, Magnus R. Buchner
{"title":"Cationic Phosphino Beryllium Scorpionates and their Reactivity as Lewis Acid–Base Pairs","authors":"Chantsalmaa Berthold, Deniz F. Bekiş, Jan Moritz, Gilles Stebens, Burkhard Butschke, Magnus R. Buchner","doi":"10.1002/ceur.202500142","DOIUrl":"https://doi.org/10.1002/ceur.202500142","url":null,"abstract":"<p>Herein, the article describes a facile and modular access to cationic beryllium phosphine complexes [TpBe(P<i>R</i><sub>3</sub>)]<sup>+</sup> (P<i>R</i><sub>3</sub> = PMe<sub>3</sub>, PEt<sub>3</sub>, PPh<sub>3</sub>, PCy<sub>3</sub>, PMe<sub>2</sub>Ph, PMePh<sub>2</sub>), which are stabilized through a monoanionic tris(pyrazolyl)borate (Tp) ligand. These tetracoordinate beryllium complex cations are characterized by NMR and IR spectroscopy as well as mass spectrometry, X-ray diffraction and quantum chemical calculations within the density functional theory framework. Furthermore, the stability of the Be<span></span>P bond strength is evaluated, and its reactivity toward chalcogens, carbon dioxide, sulfur dioxide, carbodiimides, and dihydrogen is studied.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500142","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128858","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 : 2025-07-06DOI: 10.1002/ceur.202500104
Jens Tolboom, Alexis K. Bauer, Johan Bootsma, Jitte Flapper, Michael L. Neidig, Bas de Bruin
{"title":"Advancing Light-Triggered Alkyd Paint Curing: (Cp)FeII(naphthalene)](PF6) Catalysts with Enhanced Photosensitivity and Increased Performance in Pigmented Alkyd Paints","authors":"Jens Tolboom, Alexis K. Bauer, Johan Bootsma, Jitte Flapper, Michael L. Neidig, Bas de Bruin","doi":"10.1002/ceur.202500104","DOIUrl":"https://doi.org/10.1002/ceur.202500104","url":null,"abstract":"<p>The class of photoactive complexes [(Cp)Fe<sup>II</sup>(arene)]<sup>+</sup> (Cp = cyclopentadienyl, arene = C<sub>6</sub>H<sub>6</sub>, C<sub>6</sub>H<sub>5</sub>;Me) enable light-controlled alkyd paint curing, eliminating the need for anti-skinning agents. While [(Cp)Fe<sup>II</sup>(benzene)](PF<sub>6</sub>) (0.10 wt%) initiates curing under ambient light (116 Lux/1.7 mW/m<sup>2</sup>) within 6 h for transparent paints, it is ineffective in dark-colored formulations. Here, we demonstrate that the more photosensitive complexes [(Cp)Fe<sup>II</sup>(L)](PF<sub>6</sub>) (L = naphthalene, 5-methoxynaphthalene, 6-methoxy-naphthalene, 5,8-dimethoxynaphthalene) accelerate curing with lower loadings (0.05 wt%). Due to their higher extinction coefficients and red-shifted adsorption bands, these [(Cp)Fe<sup>II</sup>(L)](PF<sub>6</sub>) catalysts effectively cure dark-pigmented paints. Mössbauer spectroscopy reveals the formation of a high-spin Fe<sup>II</sup> intermediate as the active species. TD-DFT calculations reveal a redshift in absorption, attributed to a transition from dz<sup>[</sup><sup>2</sup><sup>]</sup>-<i>d</i><sub>xy</sub>*/<i>d</i><sub>yz</sub>* (arene/naphthalene) to L<sub>π</sub>-<i>d</i><sub>xy</sub>*/<i>d</i><sub>yz</sub>* (methoxylated naphthalenes). Excitation of the complexes using wavelengths corresponding to these absorbance bands result in weakening of the Fe<sup>II</sup>-η<sup>6</sup>C<sub>6</sub> bonds, facilitating light-induced dissociation. This advancement enhances latency originating from photoactivation while expanding applicability to pigmented systems.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500104","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128868","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}
{"title":"In Situ Generation of Alkyl–λ3–Iodanes as Soft and Highly Reactive Electrophiles","authors":"Rina Katsuta, Takayuki Watanabe, Keitaro Matsuoka, Keito Watanabe, Kosuke Higashida, Tatsuhiko Yoshino, Shigeki Matsunaga","doi":"10.1002/ceur.202500154","DOIUrl":"https://doi.org/10.1002/ceur.202500154","url":null,"abstract":"<p>Hypervalent iodine compounds have found various applications in organic chemistry and related research fields. Compared with aryl-, alkynyl-, and alkenyl-substituted iodanes and iodonium salts, alkyl–λ<sup>3</sup>–iodanes have been much less studied due to their infamous instability and the lack of convenient methods for their generation. Herein, it is reported that the reaction between a tetraalkylsilane and iodine tris(trifluoroacetate) at low temperature cleanly generates the corresponding alkyl–λ<sup>3</sup>–iodane in commonly used chlorinated solvents. The in situ-generated alkyl–λ<sup>3</sup>–iodanes are reasonably stable at low temperature, and Me–λ<sup>3</sup>–iodane serves as a soft and highly electrophilic methylating agent for tertiary sulfonamides. This alkylative activation of tertiary sulfonamides provides reactive sulfonyl ammonium intermediates that can achieve transamidation and fluorination reactions, thus demonstrating the synthetic utility of the in situ-generated alkyl–λ<sup>3</sup>–iodane.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128881","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 : 2025-07-06DOI: 10.1002/ceur.202500142
Chantsalmaa Berthold, Deniz F. Bekiş, Jan Moritz, Gilles Stebens, Burkhard Butschke, Magnus R. Buchner
{"title":"Cationic Phosphino Beryllium Scorpionates and their Reactivity as Lewis Acid–Base Pairs","authors":"Chantsalmaa Berthold, Deniz F. Bekiş, Jan Moritz, Gilles Stebens, Burkhard Butschke, Magnus R. Buchner","doi":"10.1002/ceur.202500142","DOIUrl":"https://doi.org/10.1002/ceur.202500142","url":null,"abstract":"<p>Herein, the article describes a facile and modular access to cationic beryllium phosphine complexes [TpBe(P<i>R</i><sub>3</sub>)]<sup>+</sup> (P<i>R</i><sub>3</sub> = PMe<sub>3</sub>, PEt<sub>3</sub>, PPh<sub>3</sub>, PCy<sub>3</sub>, PMe<sub>2</sub>Ph, PMePh<sub>2</sub>), which are stabilized through a monoanionic tris(pyrazolyl)borate (Tp) ligand. These tetracoordinate beryllium complex cations are characterized by NMR and IR spectroscopy as well as mass spectrometry, X-ray diffraction and quantum chemical calculations within the density functional theory framework. Furthermore, the stability of the Be<span></span>P bond strength is evaluated, and its reactivity toward chalcogens, carbon dioxide, sulfur dioxide, carbodiimides, and dihydrogen is studied.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500142","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128870","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 : 2025-07-06DOI: 10.1002/ceur.202500104
Jens Tolboom, Alexis K. Bauer, Johan Bootsma, Jitte Flapper, Michael L. Neidig, Bas de Bruin
{"title":"Advancing Light-Triggered Alkyd Paint Curing: (Cp)FeII(naphthalene)](PF6) Catalysts with Enhanced Photosensitivity and Increased Performance in Pigmented Alkyd Paints","authors":"Jens Tolboom, Alexis K. Bauer, Johan Bootsma, Jitte Flapper, Michael L. Neidig, Bas de Bruin","doi":"10.1002/ceur.202500104","DOIUrl":"https://doi.org/10.1002/ceur.202500104","url":null,"abstract":"<p>The class of photoactive complexes [(Cp)Fe<sup>II</sup>(arene)]<sup>+</sup> (Cp = cyclopentadienyl, arene = C<sub>6</sub>H<sub>6</sub>, C<sub>6</sub>H<sub>5</sub>;Me) enable light-controlled alkyd paint curing, eliminating the need for anti-skinning agents. While [(Cp)Fe<sup>II</sup>(benzene)](PF<sub>6</sub>) (0.10 wt%) initiates curing under ambient light (116 Lux/1.7 mW/m<sup>2</sup>) within 6 h for transparent paints, it is ineffective in dark-colored formulations. Here, we demonstrate that the more photosensitive complexes [(Cp)Fe<sup>II</sup>(L)](PF<sub>6</sub>) (L = naphthalene, 5-methoxynaphthalene, 6-methoxy-naphthalene, 5,8-dimethoxynaphthalene) accelerate curing with lower loadings (0.05 wt%). Due to their higher extinction coefficients and red-shifted adsorption bands, these [(Cp)Fe<sup>II</sup>(L)](PF<sub>6</sub>) catalysts effectively cure dark-pigmented paints. Mössbauer spectroscopy reveals the formation of a high-spin Fe<sup>II</sup> intermediate as the active species. TD-DFT calculations reveal a redshift in absorption, attributed to a transition from dz<sup>[</sup><sup>2</sup><sup>]</sup>-<i>d</i><sub>xy</sub>*/<i>d</i><sub>yz</sub>* (arene/naphthalene) to L<sub>π</sub>-<i>d</i><sub>xy</sub>*/<i>d</i><sub>yz</sub>* (methoxylated naphthalenes). Excitation of the complexes using wavelengths corresponding to these absorbance bands result in weakening of the Fe<sup>II</sup>-η<sup>6</sup>C<sub>6</sub> bonds, facilitating light-induced dissociation. This advancement enhances latency originating from photoactivation while expanding applicability to pigmented systems.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500104","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128880","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 : 2025-06-30DOI: 10.1002/ceur.202400117
Sabrina Conoci
{"title":"The Frontier of Biosensors: The Polymerase Chain Reaction-Free Approach for Point-of-Care Devices","authors":"Sabrina Conoci","doi":"10.1002/ceur.202400117","DOIUrl":"10.1002/ceur.202400117","url":null,"abstract":"<p>The nucleic acids (NA) analysis is spread out by the invention of polymerase chain reaction (PCR). Even though the method has proven to be a disruptively innovation in the medical field, by creating a new of sector of molecular diagnostics, it however remains the prerogative of analysis of laboratories, due to its complexity and cost. To further make progresses in this sector, the development of point-of-care (POC) genetic testing technologies is crucial by offering the advantages to be fast, sensitive and specific, low cost, and, above all, able to be used onsite by nonspecialized people. In this context, the PCR-free approaches are very relevant since they do not need amplification processes and, therefore, they simplify significantly the experimental set up aimed to detect the NA. In this perspective, an overview of most innovative approaches for genetic point care technologies rapid test is presented and discussed particularly appealing to be integrated in portable and easy-to-use POC devices.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400117","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635671","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 : 2025-06-25DOI: 10.1002/ceur.202500160
Ranjini Laskar, Frank Glorius
{"title":"Rewriting Alkene Frameworks: A Practical Strategy for Nitrogen Incorporation","authors":"Ranjini Laskar, Frank Glorius","doi":"10.1002/ceur.202500160","DOIUrl":"https://doi.org/10.1002/ceur.202500160","url":null,"abstract":"<p>Expanding the reach of skeletal editing to unactivated hydrocarbons presents a formidable challenge in nitrogen incorporation chemistry. In a recent advance, Morandi and coworkers have developed a direct, metal-free strategy to insert nitrogen into simple alkenes, converting them into valuable amidines and nitriles. This transformation leverages a transient aza-allenium intermediate, formed in situ from phenyliodine(III) bis(trifluoroacetate) and ammonium carbamate, to achieve C<span></span>N bond formation under mild and open-flask conditions. The method is notable for its broad substrate scope, high yields (up to 99%), and compatibility with diverse functional groups—including esters, ketones, halides, and alcohols. Crucially, it marks a conceptual departure from earlier indole-based editing strategies by engaging electronically unbiased alkenes. Through operational simplicity and mechanistic novelty, this work defines a new direction for nitrogen insertion chemistry and opens avenues for late-stage functionalization and modular scaffold diversification.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500160","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129429","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 : 2025-06-25DOI: 10.1002/ceur.202500160
Ranjini Laskar, Frank Glorius
{"title":"Rewriting Alkene Frameworks: A Practical Strategy for Nitrogen Incorporation","authors":"Ranjini Laskar, Frank Glorius","doi":"10.1002/ceur.202500160","DOIUrl":"https://doi.org/10.1002/ceur.202500160","url":null,"abstract":"<p>Expanding the reach of skeletal editing to unactivated hydrocarbons presents a formidable challenge in nitrogen incorporation chemistry. In a recent advance, Morandi and coworkers have developed a direct, metal-free strategy to insert nitrogen into simple alkenes, converting them into valuable amidines and nitriles. This transformation leverages a transient aza-allenium intermediate, formed in situ from phenyliodine(III) bis(trifluoroacetate) and ammonium carbamate, to achieve C<span></span>N bond formation under mild and open-flask conditions. The method is notable for its broad substrate scope, high yields (up to 99%), and compatibility with diverse functional groups—including esters, ketones, halides, and alcohols. Crucially, it marks a conceptual departure from earlier indole-based editing strategies by engaging electronically unbiased alkenes. Through operational simplicity and mechanistic novelty, this work defines a new direction for nitrogen insertion chemistry and opens avenues for late-stage functionalization and modular scaffold diversification.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500160","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129430","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 : 2025-06-23DOI: 10.1002/ceur.202500121
Xu Zhang, Fushan Chen, Chen Zhu
{"title":"Radical-Mediated Sulfonylarylation of Unactivated Alkynes via Intramolecular 1,4-(hetero)aryl Migration","authors":"Xu Zhang, Fushan Chen, Chen Zhu","doi":"10.1002/ceur.202500121","DOIUrl":"https://doi.org/10.1002/ceur.202500121","url":null,"abstract":"<p>Radical-mediated difunctionalization of alkynes is an extensively explored strategy for diverse alkyne transformation and utilization. However, the direct difunctionalization of unactivated alkynes remains a significant challenge. In this study, a novel visible light-induced, redox-neutral sulfonylarylation of unactivated alkynes is reported, facilitated by a radical-mediated intramolecular 1,4-(hetero)aryl migration. Notably, this transformation enables the synthesis of a diverse array of multisubstituted vinyl sulfones, with tunable (<i>E</i>)- and (<i>Z</i>)-selectivity controlled by the wavelength of visible light. This method features mild reaction conditions, excellent regio- and stereoselectivity, and broad functional group compatibility.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500121","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129231","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}