Organic chemistry frontiers : an international journal of organic chemistry最新文献

{"title":"Light-enabled metal-free carbo- and silyl functionalization of [1.1.1]propellane and [3.1.1]propellane.","authors":"Yongchen Wang, Martin Pauze, Spencer P Pitre, Julian G West","doi":"10.1039/d6qo00901h","DOIUrl":"https://doi.org/10.1039/d6qo00901h","url":null,"abstract":"<p><p>1,3-Disubstituted bicyclo[1.1.1]pentanes (BCPs) have emerged as privileged scaffolds in pharmaceutical discovery and functional materials, often employed as bioisosteres of <i>para</i>-disubstituted benzenes. Existing synthetic approaches to these motifs typically rely on muti-step sequences or multi-component reactions and frequently require the participation of transition metals, photocatalysts and radical initiators. Herein, we report a modular and transition metal-free strategy for the synthesis of 1,3-disubstituted BCPs directly from [1.1.1]propellane through sequential C-C bond formation. The protocol enables efficient access to dichloro- and trichloro-substituted BCPs, which represent underexplored yet promising scaffolds for drug discovery. The strategy could be further extended to [3.1.1]propellane, affording 1,5-disubstituted bicyclo[3.1.1]heptanes (BCHs). Notably, this approach could also be extended to C-Si bond formation, providing rare silyl-substituted BCPs with potential applications in material science. Overall, this work establishes a general, catalyst-free platform for the modular functionalization of highly strained propellanes.</p>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13484456/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148804297","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":"Pillar[<i>n</i>]arene-based phosphine ligands: synthesis, coordination chemistry and application in selective Au(i) catalysis.","authors":"Antoine Konter, Michele Buccio, Louis Vidal, Céline Besnard, Clément Mazet","doi":"10.1039/d6qo00815a","DOIUrl":"10.1039/d6qo00815a","url":null,"abstract":"<p><p>We report a divergent and modular synthetic strategy for the functionalization of pillar[<i>n</i>]arenes, enabling the synthesis of a comprehensive library of 17 mono- and bisphosphine ligands. By leveraging a Pd-catalyzed phosphinylation of A1/A2-ditriflate-pillararenes, we demonstrate that precise stoichiometric control permits the isolation of bifunctional phosphine-triflate intermediates. These scaffolds serve as versatile pivotal intermediates for the construction of rim-differentiated bisphosphines and hybrid aryl-phosphine derivatives <i>via</i> sequential Pd-catalyzed cross-couplings. Coordination studies with gold(i) precursors, supported by X-ray crystallography, reveal a certain degree of conformational plasticity inherent to the macrocyclic backbone. The catalytic utility of these macromolecular ligands was validated in the gold(i)-catalyzed cycloisomerization of 1,6-enynes, where several derivatives exhibited excellent levels of regioselectivity.</p>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":" ","pages":"5887-5897"},"PeriodicalIF":0.0,"publicationDate":"2026-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13403166/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148611512","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":"1,4-Dihydropyrrolo[3,2-<i>b</i>]pyrrole as a new electron-donor in the construction of triarylmethyl radicals.","authors":"Bartosz Godlewski, Krzysztof Grudzień, Pavlo Aleshkevych, Beata Koszarna, Vinod K Vishwakarma, Olaf Morawski, Piotr Kaszyński, Andrzej Szewczyk, Andrzej Sobolewski, Katarzyna Rybicka-Jasińska, Daniel T Gryko","doi":"10.1039/d6qo00682e","DOIUrl":"10.1039/d6qo00682e","url":null,"abstract":"<p><p>A diverse range of triarylmethyl radicals bearing the 1,4-dihydropyrrolo[3,2-<i>b</i>]pyrrole (DHPP) scaffold and its π-expanded analogs was prepared for the first time, including a structurally unique architecture in which an electron-donating moiety and the radical center are in close through-space proximity. For the first time, triarylmethyl radicals were prepared <i>via</i> electrochemical oxidation. Compared with classical oxidation, the yields were higher. Moreover, a methodology transforming 1,4-dihydropyrrolo[3,2-<i>b</i>]pyrrole into corresponding radicals <i>via</i> Buchwald-Hartwig amination was developed. This method provides easy access to <i>N</i>-linked triarylmethyl radicals <i>via</i> a convergent protocol with complete preservation of open-shell character. Linking the tris(2,4,6-trichlorophenyl)methyl radical with various electron-donating scaffolds bearing a DHPP core revealed that the stronger the electron donor, the weaker and more bathochromically shifted was the CT band. Luminescence of these open-shell dyes, except for radical-bearing 1,4-dihydropyrrolo[3,2-<i>b</i>]indole (<i>Φ</i> _F = 1.9 × 10^-4), was below the limit of detection, which corresponded to extremely small oscillator strengths for the D₁ → D₀ transition. A clear correlation was observed between increasing ionization potentials (decreasing electron-donating strength) and <i>ε</i> values throughout the series of radicals. A diradical in which two tris(2,4,6-trichlorophenyl)methyl scaffolds were bridged with 1,4-dihydropyrrolo[3,2-<i>b</i>]pyrrole lacked emission, but it had a significantly bathochromically shifted absorption band (<i>λ</i> ^max _abs = 741 nm).</p>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-07-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13417363/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148623576","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":"Clicking acylgermanes: modular access to photoinitiators for visible-light photopolymerization.","authors":"André Culum, Julia Fuchs, Carolyn Vargas, Fabian Rath, Dagmar Brislinger, Thomas Lainer, Julian Maier, Roland C Fischer, Ana Torvisco, Anne-Marie Kelterer, Dmytro Neshchadin, Thomas Griesser, Sandro Keller, Tanja M Wrodnigg, Michael Haas","doi":"10.1039/d6qo00741d","DOIUrl":"10.1039/d6qo00741d","url":null,"abstract":"<p><p>Herein, we report a modular and biocompatible platform of Cu-catalyzed azide-alkyne cycloaddition (CuAAC)-compatible acylgermanes. Broad functional-group tolerance is demonstrated by a library of novel derivatives that were isolated and characterized by NMR, UV/Vis spectroscopy, and mass spectrometry, with selected structures confirmed by single-crystal X-ray diffraction. We also disclose the first acylgermanes bearing unprotected carbohydrate motifs, whose marked polarity enabled initial biological assessment. Representative examples showed low cytotoxicity and measurable affinity for lipid bilayers in assays with 1-palmitoyl-2-oleoyl-<i>sn-glycero</i>-3-phosphocholine (POPC) large unilamellar vesicles. Photo-DSC and photo-CIDNP experiments confirmed efficient photoinitiation and radical pathways characteristic of this class. Coupling acylgermane chemistry with robust CuAAC click methodology expands the scope of acylgermane photoinitiators, enabling rapid late-stage functionalization with diverse motifs and opening routes to complex materials and entry into biological applications.</p>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":" ","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13439046/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148681954","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":"Formal meta-selective C–H acylation of pyridines via the triplet state of oxazinopyridine intermediates","authors":"Fan Gao,&nbsp;Yajing Bian,&nbsp;Shiqing Huang,&nbsp;Xiaoyu Yan","doi":"10.1039/d6qo00478d","DOIUrl":"10.1039/d6qo00478d","url":null,"abstract":"<div><div>Pyridines are privileged structural motifs in pharmaceuticals and bioactive molecules. The introduction of substituents or functional groups at the <em>meta</em>-position <em>via</em> direct C–H functionalization of pyridines remains a formidable challenge. Herein, we report <em>meta</em>-selective acylation and sulfonylation of pyridines <em>via</em> an energy transfer (EnT) process, that activates oxazinopyridine intermediates <em>via</em> the triplet state. This strategy leverages the high reducibility of photoexcited oxazinopyridines, enabling the single-electron reduction of persistent radical precursors such as acyl and sulfonyl azolium salts. Mechanistic investigations, including photophysical experiments and DFT calculations, delineate the generation of the key triplet intermediate and elucidate a cooperative radical coupling pathway. This reaction paradigm overcomes the previous limitation to electrophilic or transient radical partners, providing a versatile platform for diverse <em>meta</em>-functionalizations of pyridine derivatives.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4023-4030"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photoredox phosphonomethylation/cyclization of alkenes enabled by an EDA complex","authors":"Yang Zheng,&nbsp;Jiayao Zheng,&nbsp;Wenxue Zhao,&nbsp;Kai Yang,&nbsp;Qingqing Chen,&nbsp;Xiaohui Wang,&nbsp;Jiahui Jia,&nbsp;Cong Du,&nbsp;Chenxu Wei,&nbsp;Fei Chen,&nbsp;Xiaobo Pan","doi":"10.1039/d6qo00468g","DOIUrl":"10.1039/d6qo00468g","url":null,"abstract":"<div><div>The phosphonomethyl unit is an important functional group in medicinal chemistry. ICH₂PO(R¹R²) is a commercially available phosphonomethylation reagent. However, the synthesis of phosphonomethyl-substituted cyclic molecules by using ICH₂PO(R¹R²) mainly relies on noble metal-catalyzed methods. Herein, the photoredox phosphonomethylation/cyclization of alkenes has been developed. Mechanistically, the electron donor–acceptor (EDA) complex formed <em>in situ</em> between ICH₂PO(R¹R²) and 1,4-diazabicyclo[2.2.2]octane (DABCO) is key to this reaction. This method does not require photocatalysts, oxidants, or reducing agents and operates under mild conditions, making it suitable for the late-stage modification of drug molecules.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4015-4022"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intramolecular through-space heavy-atom effect in multiresonant thermally activated delayed fluorescence emitters with [2.2]paracyclophane","authors":"Yan Xu,&nbsp;Hassan Hafeez,&nbsp;Wenrui Wang,&nbsp;Ifor D. W. Samuel,&nbsp;Eli Zysman-Colman","doi":"10.1039/d6qo00318d","DOIUrl":"10.1039/d6qo00318d","url":null,"abstract":"<div><div>The heavy-atom effect (HAE) is a powerful strategy to enhance spin–orbit coupling (SOC) for accelerating reverse intersystem crossing (RISC) in multiresonant thermally activated delayed fluorescence (MR-TADF) emitters, which is relevant to the performance of organic light-emitting diodes (OLEDs). Here, we demonstrate the effectiveness of a through-space HAE using a [2.2]paracyclophane (PCP) scaffold with a co-facially aligned MR-TADF emitter and bromine atom. By placing a bromine atom at pseudo-<em>ortho</em> (<em>po</em>) or pseudo-<em>meta</em> (<em>pm</em>) positions relative to the MR-TADF core, and were obtained. The two emitters have nearly identical emission spectra to the reference , yet exhibit faster <em>k</em>_RISC: 5.3 × 10⁴ s⁻¹ (<em>po</em>) and 4.1 × 10⁴ s⁻¹ (<em>pm</em>) compared to 2.8 × 10⁴ s⁻¹ (). Despite this improvement in <em>k</em>_RISC, the corresponding OLEDs showed no alleviation in efficiency roll-off and lower maximum external quantum efficiency (EQE_max). These findings suggest that a through-space HAE using a PCP is an effective strategy to accelerate <em>k</em>_RISC while largely preserving spectral purity; however, this improvement in <em>k</em>_RISC alone is insufficient to produce a superior device performance.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 3934-3943"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemically driven nickel catalysis for formal C–H amination","authors":"Gege Jiang,&nbsp;Yun Sa,&nbsp;Bingnan Wang,&nbsp;Duanyang Kong","doi":"10.1039/d6qo00461j","DOIUrl":"10.1039/d6qo00461j","url":null,"abstract":"<div><div>The C–H amination of arenes represents a streamlined approach to arylamines, yet most existing methods rely on preactivated nitrogen reagents or directing groups, limiting practicality and substrate scope. Herein, we report a nickel-catalyzed electroreductive formal C–H amination of aryl bromides with secondary amines, enabling efficient access to 4-bromomorpholinobenzene derivatives. This halogen-enabled strategy allows formal C–H amination through transient bromine removal and reinstallation. The reaction employs electricity as a traceless redox reagent, proceeds under mild conditions without stoichiometric chemical oxidants, and exhibits broad functional group tolerance. Mechanistic studies suggest that the transformation involves electrochemically generated Ni(0) species and nitrogen-centered radicals, followed by nickel-mediated C–N bond formation and subsequent bromination. The synthetic utility of this protocol is demonstrated by gram-scale reactions, diverse downstream transformations, and a concise synthesis of the pharmaceutically relevant scaffold Entospletinib.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4131-4137"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical study on the CoII/CoIII and CoII/CoIV catalytic cycles in CoII(salen)-catalyzed radical fluorination with various different NF-type fluorinating reagents","authors":"Jingwen Li,&nbsp;Mong-Feng Chiou,&nbsp;Hongli Bao","doi":"10.1039/d6qo00260a","DOIUrl":"10.1039/d6qo00260a","url":null,"abstract":"<div><div>Co^II(salen)-catalyzed radical fluorination provides a mild and efficient approach for the construction of carbon–fluorine bonds. However, the mechanistic role of different NF-type fluorinating reagents and the corresponding catalytic cycle pathways (Co^II/Co^III<em>vs.</em> Co^II/Co^IV) in the Co^II(salen)-catalyzed fluorination system remain controversial. Therefore, this work employs density functional theory (DFT) to computationally analyze the reaction mechanisms of radical fluorination involving three classes of NF-type fluorinating reagents: <em>N-tert</em>-butylfluoramide, <em>N</em>-ethyl-<em>N</em>-fluorobenzenesulfonamide, and Me₃NFPy·BF₄. The results indicate that the nature of the NF-type fluorinating reagent exerts a decisive influence on the reaction pathway. <em>N-tert</em>-butylfluoramide and <em>N</em>-ethyl-<em>N</em>-fluorobenzenesulfonamide tend to undergo single-electron oxidation with Co^II(salen), generating Co^III(salen)–F and the corresponding amidyl radical, with the reaction proceeding <em>via</em> a Co^II/Co^III cycle. In contrast, Me₃NFPy·BF₄ favors a two-electron oxidation process, directly forming the [Co^IV(salen)–F]⁺ intermediate, and the reaction proceeds through a Co^II/Co^IV cycle. Furthermore, for the hydrofluorination of unactivated alkenes involving Me₃NFPy·BF₄, the calculations not only clearly elucidate the formation pathway of Co^III(salen)–H but also confirm that the occurrence of Wagner–Meerwein rearrangement in the product is related to the presence of a substituent at the benzylic position of the substrate. Through theoretical calculations, this study provides a unified theoretical analysis of the roles of different NF-type fluorinating reagents in the Co^II(salen)-catalyzed fluorination system, offering an important theoretical basis for the rational design and condition optimization of future cobalt-catalyzed fluorination reactions.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4003-4014"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aluminium-catalysed carbonyl-selective hydrophosphinylation of α,β-unsaturated ketones","authors":"Ziyuan Pang,&nbsp;Wen Dai,&nbsp;Xiaobo Yang,&nbsp;Xiaoli Ma,&nbsp;Hongping Zhu,&nbsp;Zhi Yang","doi":"10.1039/d6qo00397d","DOIUrl":"10.1039/d6qo00397d","url":null,"abstract":"<div><div>An aluminium-catalysed carbonyl-selective hydrophosphinylation of α,β-unsaturated ketones is reported herein. Among the synthesised Schiff-base-supported non-precious metal complexes, the aluminium hydride complex exhibited outstanding catalytic activity. In contrast to conventional systems that favour conjugate addition, this catalytic system enables selective addition of dimethyl phosphine oxide to the carbonyl group, thereby altering the inherent regioselectivity of these substrates. Under mild conditions, a wide range of α,β-unsaturated ketones were efficiently converted to the desired products, and double hydrophosphinylation could also be achieved through adjustment of the reagent stoichiometry. DFT calculations provided further insight into the reaction mechanism and support a stepwise aluminium-assisted carbonyl activation pathway involving key Al–O–P intermediates. This work provides an efficient and sustainable strategy for selective C–P bond construction using main-group-metal catalysis.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"13 13","pages":"Pages 4109-4117"},"PeriodicalIF":0.0,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148503283","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}