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Rubrolides A, D, P, T, U: Total Syntheses and Antibacterial Evaluation of Highly Brominated Marine Natural Products rubbroides A, D, P, T, U:高溴化海洋天然产物的全合成及抗菌评价
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-11-28 DOI: 10.1002/ceur.202500298
Jasmin Janneschütz, Paul G. Schebek, Alexander Meyer, Celina Haller, Sophia Khom, Wolfgang R. Streit, Ifey Alio, Nina Schützenmeister
{"title":"Rubrolides A, D, P, T, U: Total Syntheses and Antibacterial Evaluation of Highly Brominated Marine Natural Products","authors":"Jasmin Janneschütz,&nbsp;Paul G. Schebek,&nbsp;Alexander Meyer,&nbsp;Celina Haller,&nbsp;Sophia Khom,&nbsp;Wolfgang R. Streit,&nbsp;Ifey Alio,&nbsp;Nina Schützenmeister","doi":"10.1002/ceur.202500298","DOIUrl":"10.1002/ceur.202500298","url":null,"abstract":"<p>Rubrolides are marine natural products with numerous biological activities. Over the last few decades, more than 20 members of this natural product class have been isolated, but their mode of action remains unknown. All compounds share a furanone core structure with β-aryl and γ-benzylidene substituents. The highly brominated rubrolides T, U, and an analog of rubrolide U are synthesized for the first time. Furthermore, the developed method enables the synthesis of natural rubrolides A, D, and P as pure <i>Z</i>-isomers. The synthetic approach employs a Suzuki-Miyaura cross-coupling reaction with a dibrominated aromatic boronic species as the key step, followed by a vinylogous Aldol condensation to introduce the second aromatic substituent. The synthesized compounds are biologically tested and show outstanding antibiofilm activity for <i>Stenotrophomonas maltophilia</i>, <i>Bacillus subtilis</i>, and <i>Staphylococcus aureus.</i> All synthesized compounds shows only negligible effects at GABA<sub>A</sub> receptors, suggesting that they are unlikely to exert neurotoxic effects at a concentration of 10 µM.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500298","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686297","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
Skeletal Editing from Pyridine to Aniline via C-Insertion and N-Isomerization 通过c -插入和n -异构化从吡啶到苯胺的骨架编辑
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-11-14 DOI: 10.1002/ceur.202500410
Yun Luo, Jing Dai, Yongchang Wei, Chang Min
{"title":"Skeletal Editing from Pyridine to Aniline via C-Insertion and N-Isomerization","authors":"Yun Luo,&nbsp;Jing Dai,&nbsp;Yongchang Wei,&nbsp;Chang Min","doi":"10.1002/ceur.202500410","DOIUrl":"10.1002/ceur.202500410","url":null,"abstract":"<p>Pyridine is a prevalent structural motif in drug molecules, and modifying the pyridine core is a widely utilized strategy for lead optimization in drug discovery. Nitrogen scanning systematically evaluates the effects of varying the nitrogen position within pyridyl isomers, including the extension of the nitrogen atom one or two bonds outside the ring, often resulting in anilines or benzonitriles. This strategy aims to bring the hydrogen-bonding site closer to the target protein, which can lead to substantial improvements in binding activity. In this study, a synthetic strategy is presented that transforms pyridines into anilines, with the original pyridine nitrogen atom externalized at either the <i>ipso</i> or <i>ortho</i> position. The approach employs a carbene insertion step prior to nitrogen isomerization, preserving the ring size and structural integrity throughout the transformation. This method demonstrates broad applicability, enabling the late-stage functionalization of a variety of natural products and pharmaceutical agents, and underscores its versatility and potential in drug discovery applications.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500410","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686110","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
One-Pot Ruthenium-Catalyzed Synthesis of Benzyl/Allyl-Halide Substituted (dihydro)naphthalenes via Radical Benzannulation 钌催化一锅法自由基苄基取代(二氢)萘的合成
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-12-16 DOI: 10.1002/ceur.202500350
Nicole S. van Leeuwen, David Vesseur, Thijmen Bonhoff, Jeffrey van Laar, Coert E. J. van Lare, Simon Mathew, Sonja Pullen, Joost N. H. Reek, Aalbert Zwijnenburg, Bas de Bruin
{"title":"One-Pot Ruthenium-Catalyzed Synthesis of Benzyl/Allyl-Halide Substituted (dihydro)naphthalenes via Radical Benzannulation","authors":"Nicole S. van Leeuwen,&nbsp;David Vesseur,&nbsp;Thijmen Bonhoff,&nbsp;Jeffrey van Laar,&nbsp;Coert E. J. van Lare,&nbsp;Simon Mathew,&nbsp;Sonja Pullen,&nbsp;Joost N. H. Reek,&nbsp;Aalbert Zwijnenburg,&nbsp;Bas de Bruin","doi":"10.1002/ceur.202500350","DOIUrl":"10.1002/ceur.202500350","url":null,"abstract":"<p>Herein, a selective, one-pot synthetic route to reactive benzyl- and allyl-halide-substituted naphthalenes and dihydronaphthalenes from easily accessible 2,3-aryl-1,3-butadiene substrates and simple halogenated alkanes, using [Cp*RuCl(PPh<sub>3</sub>)<sub>2</sub>] as the catalyst, is reported. The reaction is tolerant to various functional groups, including reactive carbonyl groups, halides, and trimethylsilyl groups. The scope of catalytic reactions can be expanded to otherwise difficult to synthesize substituted and reactive dihydronaphthalene and benzo[<i>b</i>]thiophene products. The resulting benzyl- and allyl-halide-substituted (dihydro-)naphthalene products are relevant synthons for drug synthesis, allowing for facile post-functionalization by making use of the reactive halide functionalities. Mechanistic studies are combined with density functional theory (DFT), which revealed a sequential catalytic atom transfer radical addition, radical benzannulation, and HCl elimination sequence. It is particularly noteworthy that the key transition state proceeds via a 6-<i>endo-trig</i> cyclization, in contrast to the classical 5-<i>exo</i>-trig cyclization as is normally observed for intramolecular radical additions. This cyclized intermediate subsequently undergoes HCl elimination to generate benzyl- and allyl-halide substituted (dihydro-)naphthalenes.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500350","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686187","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
Establishing Indium in Frustrated Lewis Pair Chemistry: From Synthesis to Catalytic Applications 在挫折路易斯对化学中建立铟:从合成到催化应用
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-11-22 DOI: 10.1002/ceur.202500360
Daniel N. Heuer, Jan-Hendrik Lamm, Hans-Georg Stammler, Beate Neumann, Andreas Mix, Yury V. Vishnevskiy, Norbert W. Mitzel
{"title":"Establishing Indium in Frustrated Lewis Pair Chemistry: From Synthesis to Catalytic Applications","authors":"Daniel N. Heuer,&nbsp;Jan-Hendrik Lamm,&nbsp;Hans-Georg Stammler,&nbsp;Beate Neumann,&nbsp;Andreas Mix,&nbsp;Yury V. Vishnevskiy,&nbsp;Norbert W. Mitzel","doi":"10.1002/ceur.202500360","DOIUrl":"10.1002/ceur.202500360","url":null,"abstract":"<p>In contrast to the vast majority of known frustrated Lewis pair (FLP) systems, which are based on “hard” (hard–soft acid–base, HSAB) boron-based compounds, this work is on systems containing the “soft” indium Lewis acid functions. The geminal intramolecular indium FLP <sup><i>t</i></sup>Bu<sub>2</sub>InCH<sub>2</sub>P<sup><i>t</i></sup>Bu<sub>2</sub> (<b>1</b>) was prepared from <sup><i>t</i></sup>Bu<sub>2</sub>InCl and LiCH<sub>2</sub>P<sup><i>t</i></sup>Bu<sub>2</sub>, and its pyridine adduct <sup><i>t</i></sup>Bu<sub>2</sub>In(py)CH<sub>2</sub>P<sup><i>t</i></sup>Bu<sub>2</sub> (<b>4</b>) was prepared from <sup><i>t</i></sup>Bu<sub>2</sub>InCl(py) and LiCH<sub>2</sub>P<sup><i>t</i></sup>Bu<sub>2</sub>. Both systems are unreactive toward H<sub>2</sub> but show FLP-typical reactivity toward CO<sub>2</sub> and CS<sub>2</sub>. The cyclic CO<sub>2</sub> and CS<sub>2</sub> adducts of <b>1</b> are stable at room temperature, and the CO<sub>2</sub> in the adduct can be replaced by CS<sub>2</sub>, showing that the CO<sub>2</sub> adduct formation is reversible. The catalytic activity of <b>4</b> toward CO<sub>2</sub> reduction with pinacolborane to MeOBPin was tested. While <b>4</b> shows decent turnover numbers, the turnover frequencies (TOFs) are low due to a long incubation period after the first reduction step. The formaldehyde-adduct of FLP <b>1</b> proved to be an efficient catalyst, reaching TOFs of up to 41.3 h<sup>–1</sup>, thus surpassing a previous FLP-held record of 21 h<sup>–1</sup> using pinacolborane as a reducing agent.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500360","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686253","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
Oxide Interface of Gallium-Based Liquid Metals: Beneficial Bridge or Hidden Risk? 镓基液态金属氧化物界面:有益的桥梁还是潜在的风险?
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-11-28 DOI: 10.1002/ceur.202500295
Yi Fan, Shuai Wang, Xu Hou
{"title":"Oxide Interface of Gallium-Based Liquid Metals: Beneficial Bridge or Hidden Risk?","authors":"Yi Fan,&nbsp;Shuai Wang,&nbsp;Xu Hou","doi":"10.1002/ceur.202500295","DOIUrl":"10.1002/ceur.202500295","url":null,"abstract":"<p>Oxide interfaces in gallium-based liquid metals (Ga-based LMs) are of paramount importance, given their substantial influence on the material properties and performance across a range of applications. The emergence of these interfaces presents a double-edged sword, providing both significant advantages and potential drawbacks. While a self-limiting, protective oxide layer improves wettability and functionality, it also restricts fluidity and alters the alloy's fundamental properties. Therefore, understanding the dual role of oxide interfaces—as both a protective barrier and a potential risk—is essential for optimizing its application in fields such as flexible electronics, energy conversion, catalysis, and bioengineering. This article reviews the mechanisms behind oxidation, regulation techniques, and the interactions and reactivity at oxide interfaces. By examining their roles in both enhancing and restricting the performance of Ga-based LMs, insights into the delicate balance necessary to maximize benefits while mitigating risks in practical applications are offered.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500295","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686236","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
Metal-Free Covalent Organic Frameworks for Photocatalytic CO2 Reduction 光催化CO2还原的无金属共价有机框架
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-11-27 DOI: 10.1002/ceur.202500176
Supriti Dutta, Akhtar Alam, Pekham Chakrabortty, Pradip Pachfule
{"title":"Metal-Free Covalent Organic Frameworks for Photocatalytic CO2 Reduction","authors":"Supriti Dutta,&nbsp;Akhtar Alam,&nbsp;Pekham Chakrabortty,&nbsp;Pradip Pachfule","doi":"10.1002/ceur.202500176","DOIUrl":"10.1002/ceur.202500176","url":null,"abstract":"<p>Carbon dioxide (CO<sub>2</sub>), a major greenhouse gas, is undoubtedly in urgent need of mitigation as its concentration in the atmosphere is rising at an alarming rate, leading to numerous environmental consequences, most notably the serious problem of climate change. Researchers are, therefore, looking for different ways to reduce carbon dioxide. In this article, the use of atmospheric CO<sub>2</sub> gas as a C1 feedstock is a prominent approach, as the effective conversion of CO<sub>2</sub> into fuels can provide a viable option to produce several industrial organic fuels. Among the various types of photocatalysts, covalent organic frameworks (COFs) have garnered significant interest because of their well-defined structures, durable frameworks, intrinsic porosity, and promising photocatalytic performance. Consequently, extensive research has been conducted to explore the photocatalytic capabilities of COFs in the field of CO<sub>2</sub> reduction. Therefore, this comprehensive article highlights the latest developments and advances in metal-free COF-based photocatalytic CO<sub>2</sub> reduction. It also outlines and compares different types of linkers used as COF building blocks, which are highly efficient in the CO<sub>2</sub> reduction reaction. The article concludes with an overview of the current challenges and potential directions for future research in the field of COF-based photocatalysis.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500176","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686231","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
Organophotoredox/Cobalt-Catalyzed Retro-Hydroformylation of Aldehydes 有机光氧化还原/钴催化醛的反氢甲酰化
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-11-20 DOI: 10.1002/ceur.202500408
Augustin Nouaille, Emmanuel Magnier, Corinne Gosmini, Guillaume Dagousset
{"title":"Organophotoredox/Cobalt-Catalyzed Retro-Hydroformylation of Aldehydes","authors":"Augustin Nouaille,&nbsp;Emmanuel Magnier,&nbsp;Corinne Gosmini,&nbsp;Guillaume Dagousset","doi":"10.1002/ceur.202500408","DOIUrl":"10.1002/ceur.202500408","url":null,"abstract":"<p>A new cobalt/organophotoredox dual catalytic system is reported for the efficient retro-hydroformylation of aldehydes. Under the optimized conditions, a wide range of α-monosubstituted aldehydes are readily transformed into the desired alkenes in a one-pot two-step process, via the in situ formation of the corresponding 1,4-dihydropyridines as key intermediates. This strategy represents a mild alternative to other traditional approaches requiring high temperatures and noble metal catalysts.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500408","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686213","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
A Crystallographic Shear Driven by Oxygen Insertion in (LuFeO3)nLuFe2O4 氧插入驱动的(LuFeO3)nLuFe2O4晶体剪切
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-12-01 DOI: 10.1002/ceur.202500349
Tianyu Li, Stephanie J. Hong, Sz-Chian Liou, Emily Foley, Hadas Elazar-Mittelman, Xiuquan Zhou, H. Cein Mandujano, Efrain E. Rodriguez
{"title":"A Crystallographic Shear Driven by Oxygen Insertion in (LuFeO3)nLuFe2O4","authors":"Tianyu Li,&nbsp;Stephanie J. Hong,&nbsp;Sz-Chian Liou,&nbsp;Emily Foley,&nbsp;Hadas Elazar-Mittelman,&nbsp;Xiuquan Zhou,&nbsp;H. Cein Mandujano,&nbsp;Efrain E. Rodriguez","doi":"10.1002/ceur.202500349","DOIUrl":"10.1002/ceur.202500349","url":null,"abstract":"<p>Herein, a structural shearing behavior in heterolayered (LuFeO<sub>3</sub>)<sub><i>n</i></sub>LuFe<sub>2</sub>O<sub>4</sub> (<i>n</i> = 0, 1) upon oxygen uptake is reported. Using advanced X-ray and electron diffraction techniques, it is found that when (LuFeO<sub>3</sub>)<sub><i>n</i></sub>LuFe<sub>2</sub>O<sub>4</sub> absorbs oxygen, only the LuFe<sub>2</sub>O<sub>4</sub> layer is affected, transforming into LuFe<sub>2</sub>O<sub>4.5</sub>, while the LuFeO<sub>3</sub> layer remains chemically unchanged. Magnetic susceptibility and Mössbauer spectroscopy corroborate this local oxygen uptake in the LuFe<sub>2</sub>O<sub>4</sub> layer by confirming the mixed oxidation state of the iron site. Interestingly, even though the LuFeO<sub>3</sub> layer in the <i>n</i> = 1 compound does not directly absorb oxygen, it significantly influences how the structure evolves during oxidation. The <i>n</i> = 1 compound (Lu<sub>2</sub>Fe<sub>3</sub>O<sub>7</sub>) is active for oxygen absorption at a lower temperature than the <i>n</i> = 0 compound LuFe<sub>2</sub>O<sub>4</sub> (110 °C vs. 150 °C from thermal gravimetric measurement). The LuFeO<sub>3</sub> layer in Lu<sub>2</sub>Fe<sub>3</sub>O<sub>7</sub> acts as a buffer zone that reduces strain and chemical pressure within the LuFe<sub>2</sub>O<sub>4</sub> layer thereby enhancing the rate of oxygen absorption. The findings reveal a common behavior in the (LuFeO<sub>3</sub>)<sub><i>n</i></sub>LuFe<sub>2</sub>O<sub>4</sub> series that provides new insights into the design of ternary oxides active at low temperatures for fast oxygen uptake. This crystallographic study can therefore lead to further improvements in the oxygen storage capability and oxygen absorption rates.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500349","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686821","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
Electrophilic Functionalization of Donor-Stabilized Phosphanylboranes: A New Pathway toward Heavy 13/14/15 Parent Hydride-Containing Compounds 供体稳定磷酰硼烷的亲电功能化:制备重13/14/15亲氢化合物的新途径
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-12-18 DOI: 10.1002/ceur.202500409
Robert Szlosek, Michael Seidl, Christoph Riesinger, Lisa Zimmermann, Amelie Sophie Niefanger, Christian Marquardt, Alexey Y. Timoshkin, Manfred Scheer
{"title":"Electrophilic Functionalization of Donor-Stabilized Phosphanylboranes: A New Pathway toward Heavy 13/14/15 Parent Hydride-Containing Compounds","authors":"Robert Szlosek,&nbsp;Michael Seidl,&nbsp;Christoph Riesinger,&nbsp;Lisa Zimmermann,&nbsp;Amelie Sophie Niefanger,&nbsp;Christian Marquardt,&nbsp;Alexey Y. Timoshkin,&nbsp;Manfred Scheer","doi":"10.1002/ceur.202500409","DOIUrl":"10.1002/ceur.202500409","url":null,"abstract":"<p>A novel method for the functionalization of donor-stabilized 13/15 compounds is presented. Reacting the IDipp (1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) stabilized parent phosphanylborane IDipp·BH<sub>2</sub>PH<sub>2</sub> with (in situ generated) main group electrophiles results in mixed 13/14/15 compounds [IDipp·BH<sub>2</sub>PH<sub>2</sub>ER<sub>3</sub>][WCA] (WCA = weakly coordinating anion, ER<sub>3</sub> = CH<sub>3</sub> (<b>2</b>), SiEt<sub>3</sub> (<b>3</b>), Ge(SiMe<sub>3</sub>)<sub>3</sub> (<b>4</b>), SnMe<sub>3</sub> (<b>5</b>)) containing the complete series from carbon to tin. In contrast, reactions with the group 15 electrophiles [Cy<sub>2</sub><i>Pn</i>][PF<sub>6</sub>] (<i>Pn</i> = P, As) yielded an intriguing P–P coupling reaction, affording [IDipp·BH<sub>2</sub>PH<sub>2</sub>PHBH<sub>2</sub>·IDipp][PF<sub>6</sub>] (<b>6</b>). The protonated phosphanylboranes reveal acidic protons at the phosphorus atom, and this can be exploited by reactions with LiGaH<sub>4</sub> and LiAlH<sub>4</sub>, resulting in either deprotonation to the parent phosphanylborane or chain extension to yield <i>LB</i>·BH<sub>2</sub>PH<sub>2</sub>GaH<sub>3</sub> (<i>LB</i> = IDipp (<b>7a</b>), Me<sub>3</sub>N (<b>7b</b>)), the first examples of a {GaH<sub>3</sub>} unit bound to a primary phosphine. The products can be characterized by multinuclear NMR spectroscopy and single-crystal X-ray structure determination.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500409","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686157","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
Covalent Attachment of a Platinum(II) Complex inside DNA Duplexes DNA双链内铂(II)配合物的共价附着
ChemistryEurope Pub Date : 2026-04-09 Epub Date: 2025-12-01 DOI: 10.1002/ceur.202500416
Tim Schäfer, Iván Maisuls, Felix Boisten, Marian Hebenbrock, Alexander Hepp, Cristian A. Strassert, Jens Müller
{"title":"Covalent Attachment of a Platinum(II) Complex inside DNA Duplexes","authors":"Tim Schäfer,&nbsp;Iván Maisuls,&nbsp;Felix Boisten,&nbsp;Marian Hebenbrock,&nbsp;Alexander Hepp,&nbsp;Cristian A. Strassert,&nbsp;Jens Müller","doi":"10.1002/ceur.202500416","DOIUrl":"10.1002/ceur.202500416","url":null,"abstract":"<p>An organometallic phosphorescent Pt<sup>II</sup> complex is introduced into DNA duplexes via oxidative addition to a tailor-made artificial nucleobase, acting as an N^N^C donor ligand. Its covalent attachment to the nucleic acid backbone localizes the metal ion in the center of the duplex. The platination exerts a stabilizing effect of up to 6.4 °C on the duplex, with the degree of stabilization depending on the identity of the nucleobase in the complementary position. No interstrand crosslink is formed, as indicated by mass-spectrometry and corroborated by almost identical photoluminescence lifetimes (<i>τ</i>) in Ar-purged solution. In air-equilibrated solution, <i>τ</i> shows moderate dependence on the complementary nucleobase, suggesting that the latter influences oxygen accessibility to the luminophore. When two Pt<sup>II</sup> complexes are incorporated in neighboring positions, a redshifted luminescence from aggregates is observed in addition to monomer emission, indicating Pt···Pt interactions along the helical axis. The approach presented here allows the site-specific incorporation of highly stable Pt<sup>II</sup> complexes as phosphorescent tags into nucleic acids.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"4 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500416","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686725","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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