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Programmable Site-Selectivity: pH-Modulated Triazine–Thiol Exchange for Site- and Chemoselective Cysteine Labeling 可编程的位点选择性：ph调制三嗪-硫醇交换的位点和化学选择性半胱氨酸标记
ChemistryEurope Pub Date : 2025-08-08 DOI: 10.1002/ceur.202500273
Katerina Gavriel, Daniel Deißenbeck, Thomas J. Rutjes, Daniëlle W. T. Geers, Jan Meisner, Kevin Neumann
{"title":"Programmable Site-Selectivity: pH-Modulated Triazine–Thiol Exchange for Site- and Chemoselective Cysteine Labeling","authors":"Katerina Gavriel,&nbsp;Daniel Deißenbeck,&nbsp;Thomas J. Rutjes,&nbsp;Daniëlle W. T. Geers,&nbsp;Jan Meisner,&nbsp;Kevin Neumann","doi":"10.1002/ceur.202500273","DOIUrl":"https://doi.org/10.1002/ceur.202500273","url":null,"abstract":"<p>The chemical modification of peptides is a powerful method to enhance their pharmacological properties, including membrane permeability, metabolic stability, and binding affinity. Over recent decades, advances in chemoselective modifications have enabled the construction of well-defined peptide scaffolds with uniform and precise molecular architectures. However, beyond chemoselectivity, achieving true site-selectivity by differentiating between identical amino acids at distinct positions within complex peptide scaffolds remains a key challenge. So far, site-selectivity of cysteine labeling has been largely restricted to <i>N</i>-terminal cysteines. Herein, a programmable strategy for site-selective cysteine modifications is reported, ultimately enabling precise control over the location of cysteine functionalization within peptides. This is accomplished by employing a triazine–thiol exchange, a dynamic covalent reaction with pH-adjustable site-selectivity. It is shown that under acidic conditions internal cysteines are modified while preserving the <i>N</i>-terminal cysteine functionality. Conversely, at neutral pH, site-selective modification of <i>N</i>-terminal cysteines is achieved. The modification of <i>N</i>-terminal cysteines using triazine–thiol exchange proceeds via an S–N shift, which converts the dynamic linkage into an irreversible modification. Density functional theory computations reveal that the site-selectivity originates from modulation of the formed intermediate, providing insights for future mechanism-based designs of site-selective peptide chemistries. The here presented methodology allows chemists to gain control over site-selectivity and unlock new possibilities for precision peptide engineering.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500273","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128944","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}
引用次数: 0
Advances in Enaminomaleimides Chemistry: Synthesis, Chemical Applications, and Perspectives 漆胺酰亚胺化学研究进展：合成、化学应用及展望
ChemistryEurope Pub Date : 2025-08-08 DOI: 10.1002/ceur.202500220
Adrián López-Francés, Birane Diop, Xingyu Jiang, Jean Rodriguez, Muriel Amatore, Thierry Constantieux
{"title":"Advances in Enaminomaleimides Chemistry: Synthesis, Chemical Applications, and Perspectives","authors":"Adrián López-Francés,&nbsp;Birane Diop,&nbsp;Xingyu Jiang,&nbsp;Jean Rodriguez,&nbsp;Muriel Amatore,&nbsp;Thierry Constantieux","doi":"10.1002/ceur.202500220","DOIUrl":"https://doi.org/10.1002/ceur.202500220","url":null,"abstract":"<p>Interest in enaminomaleimides has grown significantly over the past decades, as they have proven to be versatile building blocks for the synthesis of functionalized heterocycles. Their unique nucleophilic character, in contrast to the classical electrophilic nature of maleimides, has unlocked new synthetic possibilities, enabling their application across a wide range of chemical transformations. Moreover, their potential extends beyond synthetic chemistry, with promising results reported in both materials science and medicinal chemistry. This review provides a comprehensive overview of the synthesis and chemical applications of enaminomaleimides over time, while also highlighting emerging trends and future directions in this rapidly evolving field.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500220","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128946","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}
引用次数: 0
Advances in Enaminomaleimides Chemistry: Synthesis, Chemical Applications, and Perspectives 漆胺酰亚胺化学研究进展：合成、化学应用及展望
ChemistryEurope Pub Date : 2025-08-08 DOI: 10.1002/ceur.202500220
Adrián López-Francés, Birane Diop, Xingyu Jiang, Jean Rodriguez, Muriel Amatore, Thierry Constantieux
{"title":"Advances in Enaminomaleimides Chemistry: Synthesis, Chemical Applications, and Perspectives","authors":"Adrián López-Francés,&nbsp;Birane Diop,&nbsp;Xingyu Jiang,&nbsp;Jean Rodriguez,&nbsp;Muriel Amatore,&nbsp;Thierry Constantieux","doi":"10.1002/ceur.202500220","DOIUrl":"https://doi.org/10.1002/ceur.202500220","url":null,"abstract":"<p>Interest in enaminomaleimides has grown significantly over the past decades, as they have proven to be versatile building blocks for the synthesis of functionalized heterocycles. Their unique nucleophilic character, in contrast to the classical electrophilic nature of maleimides, has unlocked new synthetic possibilities, enabling their application across a wide range of chemical transformations. Moreover, their potential extends beyond synthetic chemistry, with promising results reported in both materials science and medicinal chemistry. This review provides a comprehensive overview of the synthesis and chemical applications of enaminomaleimides over time, while also highlighting emerging trends and future directions in this rapidly evolving field.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500220","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128942","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}
引用次数: 0
Research Progress in the Mechanical Enhancement of Polymer-Based Electrolytes for Lithium and Zinc Metal Batteries 锂、锌金属电池用聚合物基电解质力学增强研究进展
ChemistryEurope Pub Date : 2025-08-08 DOI: 10.1002/ceur.202500127
Zihan Wang, Yong Wang, Yan Huang
{"title":"Research Progress in the Mechanical Enhancement of Polymer-Based Electrolytes for Lithium and Zinc Metal Batteries","authors":"Zihan Wang,&nbsp;Yong Wang,&nbsp;Yan Huang","doi":"10.1002/ceur.202500127","DOIUrl":"https://doi.org/10.1002/ceur.202500127","url":null,"abstract":"<p>Lithium (Li) and zinc (Zn) metals are promising anode materials for next generation rechargeable metal batteries due to their high theoretical capacities and excellent electrical conductivity. However, uncontrolled dendrite growth can lead to rapid capacity decay, poor electrochemical stability, and limited cycle life. Polymer-based electrolytes with high mechanical strength offer a viable solution. This mini-review begins with an overview of the challenges of polymer-based electrolytes for Li and Zn metal batteries due to insufficient mechanical properties. It then explores recent advancements in the mechanical enhancement strategies. Finally, perspectives on current challenges and future research directions are provided.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500127","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128943","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}
引用次数: 0
Research Progress in the Mechanical Enhancement of Polymer-Based Electrolytes for Lithium and Zinc Metal Batteries 锂、锌金属电池用聚合物基电解质力学增强研究进展
ChemistryEurope Pub Date : 2025-08-08 DOI: 10.1002/ceur.202500127
Zihan Wang, Yong Wang, Yan Huang
{"title":"Research Progress in the Mechanical Enhancement of Polymer-Based Electrolytes for Lithium and Zinc Metal Batteries","authors":"Zihan Wang,&nbsp;Yong Wang,&nbsp;Yan Huang","doi":"10.1002/ceur.202500127","DOIUrl":"https://doi.org/10.1002/ceur.202500127","url":null,"abstract":"<p>Lithium (Li) and zinc (Zn) metals are promising anode materials for next generation rechargeable metal batteries due to their high theoretical capacities and excellent electrical conductivity. However, uncontrolled dendrite growth can lead to rapid capacity decay, poor electrochemical stability, and limited cycle life. Polymer-based electrolytes with high mechanical strength offer a viable solution. This mini-review begins with an overview of the challenges of polymer-based electrolytes for Li and Zn metal batteries due to insufficient mechanical properties. It then explores recent advancements in the mechanical enhancement strategies. Finally, perspectives on current challenges and future research directions are provided.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500127","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128945","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}
引用次数: 0
Programmable Site-Selectivity: pH-Modulated Triazine–Thiol Exchange for Site- and Chemoselective Cysteine Labeling 可编程的位点选择性：ph调制三嗪-硫醇交换的位点和化学选择性半胱氨酸标记
ChemistryEurope Pub Date : 2025-08-08 DOI: 10.1002/ceur.202500273
Katerina Gavriel, Daniel Deißenbeck, Thomas J. Rutjes, Daniëlle W. T. Geers, Jan Meisner, Kevin Neumann
{"title":"Programmable Site-Selectivity: pH-Modulated Triazine–Thiol Exchange for Site- and Chemoselective Cysteine Labeling","authors":"Katerina Gavriel,&nbsp;Daniel Deißenbeck,&nbsp;Thomas J. Rutjes,&nbsp;Daniëlle W. T. Geers,&nbsp;Jan Meisner,&nbsp;Kevin Neumann","doi":"10.1002/ceur.202500273","DOIUrl":"https://doi.org/10.1002/ceur.202500273","url":null,"abstract":"<p>The chemical modification of peptides is a powerful method to enhance their pharmacological properties, including membrane permeability, metabolic stability, and binding affinity. Over recent decades, advances in chemoselective modifications have enabled the construction of well-defined peptide scaffolds with uniform and precise molecular architectures. However, beyond chemoselectivity, achieving true site-selectivity by differentiating between identical amino acids at distinct positions within complex peptide scaffolds remains a key challenge. So far, site-selectivity of cysteine labeling has been largely restricted to <i>N</i>-terminal cysteines. Herein, a programmable strategy for site-selective cysteine modifications is reported, ultimately enabling precise control over the location of cysteine functionalization within peptides. This is accomplished by employing a triazine–thiol exchange, a dynamic covalent reaction with pH-adjustable site-selectivity. It is shown that under acidic conditions internal cysteines are modified while preserving the <i>N</i>-terminal cysteine functionality. Conversely, at neutral pH, site-selective modification of <i>N</i>-terminal cysteines is achieved. The modification of <i>N</i>-terminal cysteines using triazine–thiol exchange proceeds via an S–N shift, which converts the dynamic linkage into an irreversible modification. Density functional theory computations reveal that the site-selectivity originates from modulation of the formed intermediate, providing insights for future mechanism-based designs of site-selective peptide chemistries. The here presented methodology allows chemists to gain control over site-selectivity and unlock new possibilities for precision peptide engineering.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500273","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128941","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}
引用次数: 0
Increasing the Lewis Acidity of Pyramidal Boranes: Cationic 9-Bora-1-Azatriptycenes as Strong Boron Lewis Superacids 提高锥体硼烷的刘易斯酸：阳离子9-硼-1-氮杂三烯作为强硼刘易斯超强酸
ChemistryEurope Pub Date : 2025-08-06 DOI: 10.1002/ceur.202500100
Nicolas Niessen, Loïc Mineur, Aurélien Chardon, Arnaud Osi, Abel Idrice Adjieufack, Damien Mahaut, Nikolay Tumanov, Johan Wouters, Benoît Champagne, Guillaume Berionni
{"title":"Increasing the Lewis Acidity of Pyramidal Boranes: Cationic 9-Bora-1-Azatriptycenes as Strong Boron Lewis Superacids","authors":"Nicolas Niessen,&nbsp;Loïc Mineur,&nbsp;Aurélien Chardon,&nbsp;Arnaud Osi,&nbsp;Abel Idrice Adjieufack,&nbsp;Damien Mahaut,&nbsp;Nikolay Tumanov,&nbsp;Johan Wouters,&nbsp;Benoît Champagne,&nbsp;Guillaume Berionni","doi":"10.1002/ceur.202500100","DOIUrl":"https://doi.org/10.1002/ceur.202500100","url":null,"abstract":"<p>Bora-azatriptycenes have been synthesized and used as geminal pyridine–boranes pairs, which exhibit unusual binding modes with weakly coordinating anions, to unique aza-triptycene/bora-triptycene Lewis adducts, and to bis-triptycenes dimers with unprecedented architectural motifs. Embedding a boron atom at the edge of a triptycene scaffold, in a strongly pyramidalized and geometrically constrained environment, and protonation of the adjacent pyridine ring strongly enhances the Lewis acidity of the boron atom. High levels of Lewis acidity are reached at the boron atom of these cationic boron Lewis superacids. Experimental and quantum-chemistry screening of their Lewis acidity enables elucidation of the interplay between Lewis acidity, pyramidalization angle, reorganization energy, and charge position in the adjacent pyridinium ring, and identifies new dicationic Lewis superacids.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500100","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128840","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}
引用次数: 0
Increasing the Lewis Acidity of Pyramidal Boranes: Cationic 9-Bora-1-Azatriptycenes as Strong Boron Lewis Superacids 提高锥体硼烷的刘易斯酸：阳离子9-硼-1-氮杂三烯作为强硼刘易斯超强酸
ChemistryEurope Pub Date : 2025-08-06 DOI: 10.1002/ceur.202500100
Nicolas Niessen, Loïc Mineur, Aurélien Chardon, Arnaud Osi, Abel Idrice Adjieufack, Damien Mahaut, Nikolay Tumanov, Johan Wouters, Benoît Champagne, Guillaume Berionni
{"title":"Increasing the Lewis Acidity of Pyramidal Boranes: Cationic 9-Bora-1-Azatriptycenes as Strong Boron Lewis Superacids","authors":"Nicolas Niessen,&nbsp;Loïc Mineur,&nbsp;Aurélien Chardon,&nbsp;Arnaud Osi,&nbsp;Abel Idrice Adjieufack,&nbsp;Damien Mahaut,&nbsp;Nikolay Tumanov,&nbsp;Johan Wouters,&nbsp;Benoît Champagne,&nbsp;Guillaume Berionni","doi":"10.1002/ceur.202500100","DOIUrl":"https://doi.org/10.1002/ceur.202500100","url":null,"abstract":"<p>Bora-azatriptycenes have been synthesized and used as geminal pyridine–boranes pairs, which exhibit unusual binding modes with weakly coordinating anions, to unique aza-triptycene/bora-triptycene Lewis adducts, and to bis-triptycenes dimers with unprecedented architectural motifs. Embedding a boron atom at the edge of a triptycene scaffold, in a strongly pyramidalized and geometrically constrained environment, and protonation of the adjacent pyridine ring strongly enhances the Lewis acidity of the boron atom. High levels of Lewis acidity are reached at the boron atom of these cationic boron Lewis superacids. Experimental and quantum-chemistry screening of their Lewis acidity enables elucidation of the interplay between Lewis acidity, pyramidalization angle, reorganization energy, and charge position in the adjacent pyridinium ring, and identifies new dicationic Lewis superacids.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500100","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128861","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}
引用次数: 0
Mechanistic Study of the Light-Initiated Generation of Free Diazoalkanes: Towards Photo-Orthogonal Synthesis 光引发生成游离重氮烷烃的机理研究：走向光正交合成
ChemistryEurope Pub Date : 2025-08-02 DOI: 10.1002/ceur.202500133
Ferdinand L. Pointner, Jonas Poll, Elina K. Taskinen, Vincent George, Tristan Ruff, Florian Rott, Gabriel Mayer, Niklas Gessner, Roger-Jan Kutta, Burkhard König, Patrick Nuernberger, Christian Ochsenfeld, Regina de Vivie-Riedle
{"title":"Mechanistic Study of the Light-Initiated Generation of Free Diazoalkanes: Towards Photo-Orthogonal Synthesis","authors":"Ferdinand L. Pointner,&nbsp;Jonas Poll,&nbsp;Elina K. Taskinen,&nbsp;Vincent George,&nbsp;Tristan Ruff,&nbsp;Florian Rott,&nbsp;Gabriel Mayer,&nbsp;Niklas Gessner,&nbsp;Roger-Jan Kutta,&nbsp;Burkhard König,&nbsp;Patrick Nuernberger,&nbsp;Christian Ochsenfeld,&nbsp;Regina de Vivie-Riedle","doi":"10.1002/ceur.202500133","DOIUrl":"https://doi.org/10.1002/ceur.202500133","url":null,"abstract":"<p>An in-depth mechanistic study for the photogeneration of free diazoalkanes from <i>N</i>-tosylhydrazone precursors by combining observations from synthesis with spectroscopic and theoretical methods is presented. The <i>N</i>-tosylhydrazones have been previously established as donors for alkyl diazo species upon light irradiation, but exact mechanistic details of this photodissociation have remained elusive. Investigations of cyclohexane tosylhydrazone (CyNNTsH) by time-resolved FTIR spectroscopy proved the role of the deprotonated CyNNTs<sup>−</sup> as the light-harvesting species and revealed an intricate dependency of the thermal lifetime of the resulting diazoalkane on the deprotonating base. Computational studies including multiple approaches and levels of theory as well as rigorous benchmarking elucidated the dissociation mechanism via an allowed charge transfer state, a resulting destabilization of the dissociating bond, and a fast change of electronic character of the S<sub>1</sub>. These insights allow to suggest specific reaction conditions for photolabile or previously incompatible reaction partners thus paving way towards photo-orthogonal synthetic strategies.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500133","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128781","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}
引用次数: 0
Mechanistic Study of the Light-Initiated Generation of Free Diazoalkanes: Towards Photo-Orthogonal Synthesis 光引发生成游离重氮烷烃的机理研究：走向光正交合成
ChemistryEurope Pub Date : 2025-08-02 DOI: 10.1002/ceur.202500133
Ferdinand L. Pointner, Jonas Poll, Elina K. Taskinen, Vincent George, Tristan Ruff, Florian Rott, Gabriel Mayer, Niklas Gessner, Roger-Jan Kutta, Burkhard König, Patrick Nuernberger, Christian Ochsenfeld, Regina de Vivie-Riedle
{"title":"Mechanistic Study of the Light-Initiated Generation of Free Diazoalkanes: Towards Photo-Orthogonal Synthesis","authors":"Ferdinand L. Pointner,&nbsp;Jonas Poll,&nbsp;Elina K. Taskinen,&nbsp;Vincent George,&nbsp;Tristan Ruff,&nbsp;Florian Rott,&nbsp;Gabriel Mayer,&nbsp;Niklas Gessner,&nbsp;Roger-Jan Kutta,&nbsp;Burkhard König,&nbsp;Patrick Nuernberger,&nbsp;Christian Ochsenfeld,&nbsp;Regina de Vivie-Riedle","doi":"10.1002/ceur.202500133","DOIUrl":"https://doi.org/10.1002/ceur.202500133","url":null,"abstract":"<p>An in-depth mechanistic study for the photogeneration of free diazoalkanes from <i>N</i>-tosylhydrazone precursors by combining observations from synthesis with spectroscopic and theoretical methods is presented. The <i>N</i>-tosylhydrazones have been previously established as donors for alkyl diazo species upon light irradiation, but exact mechanistic details of this photodissociation have remained elusive. Investigations of cyclohexane tosylhydrazone (CyNNTsH) by time-resolved FTIR spectroscopy proved the role of the deprotonated CyNNTs<sup>−</sup> as the light-harvesting species and revealed an intricate dependency of the thermal lifetime of the resulting diazoalkane on the deprotonating base. Computational studies including multiple approaches and levels of theory as well as rigorous benchmarking elucidated the dissociation mechanism via an allowed charge transfer state, a resulting destabilization of the dissociating bond, and a fast change of electronic character of the S<sub>1</sub>. These insights allow to suggest specific reaction conditions for photolabile or previously incompatible reaction partners thus paving way towards photo-orthogonal synthetic strategies.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500133","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128779","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}
引用次数: 0
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