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

A one carbon linchpin for Rh(iii)-catalyzed, C(sp³)-directed C-H annulation. Rh（iii）催化，C（sp3）导向碳氢环化的单碳关键。

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-09-29 DOI: 10.1039/d6qo01119e

Michael R Hollerbach, Eleda V Plouch, Samantha M Velazquez, Simon B Blakey

引用次数: 0

Thiazination of N-substituted indole-4,7-quinones and its application in the first total synthesis of the marine natural product macrophilone E. n -取代吲哚-4,7-醌的噻嗪化及其在海洋天然产物巨philone E的首次全合成中的应用。

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-09-24 DOI: 10.1039/d6qo00838k

Manikandan Palani, Soniya Joseph, Vignesh Venkatesan, Ravikrishna Dada, Abhishek Govindan, Sadanandan E Velu

引用次数: 0

Light-enabled metal-free carbo- and silyl functionalization of [1.1.1]propellane and [3.1.1]propellane. [1.1.1]和[3.1.1]推进剂的轻致能无金属碳基和硅基功能化。

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-08-11 eCollection Date: 2026-09-29 DOI: 10.1039/d6qo00901h

Yongchen Wang, Martin Pauze, Spencer P Pitre, Julian G West

{"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":"10.1039/d6qo00901h","url":null,"abstract":"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 para-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.","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":" ","pages":"6593-6602"},"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}

引用次数: 0

Pillar[n]arene-based phosphine ligands: synthesis, coordination chemistry and application in selective Au(i) catalysis. 柱[n]芳烃基膦配体：合成、配位化学及其在选择性Au(i)催化中的应用。

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-20 eCollection Date: 2026-08-25 DOI: 10.1039/d6qo00815a

Antoine Konter, Michele Buccio, Louis Vidal, Céline Besnard, Clément Mazet

引用次数: 0

1,4-Dihydropyrrolo[3,2-b]pyrrole as a new electron-donor in the construction of triarylmethyl radicals. 1,4-二氢吡咯[3,2-b]吡咯在三芳基甲基自由基构建中的新电子给体。

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-20 eCollection Date: 2026-09-16 DOI: 10.1039/d6qo00682e

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

{"title":"1,4-Dihydropyrrolo[3,2-b]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":"A diverse range of triarylmethyl radicals bearing the 1,4-dihydropyrrolo[3,2-b]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 via electrochemical oxidation. Compared with classical oxidation, the yields were higher. Moreover, a methodology transforming 1,4-dihydropyrrolo[3,2-b]pyrrole into corresponding radicals via Buchwald-Hartwig amination was developed. This method provides easy access to N-linked triarylmethyl radicals via 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-b]indole (Φ 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 ε 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-b]pyrrole lacked emission, but it had a significantly bathochromically shifted absorption band (λ max abs = 741 nm).","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":" ","pages":"6011-6025"},"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}

引用次数: 0

Clicking acylgermanes: modular access to photoinitiators for visible-light photopolymerization. 点击酰基日耳曼：可见光光聚合的光引发剂的模块化访问。

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-15 eCollection Date: 2026-09-16 DOI: 10.1039/d6qo00741d

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

{"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":"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-sn-glycero-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.","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":" ","pages":"6126-6138"},"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}

引用次数: 0

Formal meta-selective C–H acylation of pyridines via the triplet state of oxazinopyridine intermediates 通过恶氮吡啶中间体的三重态对吡啶的正式间选择性C-H酰化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-15 DOI: 10.1039/d6qo00478d

Fan Gao, Yajing Bian, Shiqing Huang, Xiaoyu Yan

{"title":"Formal meta-selective C–H acylation of pyridines via the triplet state of oxazinopyridine intermediates","authors":"Fan Gao, Yajing Bian, Shiqing Huang, 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 meta-position via direct C–H functionalization of pyridines remains a formidable challenge. Herein, we report meta-selective acylation and sulfonylation of pyridines via an energy transfer (EnT) process, that activates oxazinopyridine intermediates via 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 meta-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}

引用次数: 0

Photoredox phosphonomethylation/cyclization of alkenes enabled by an EDA complex EDA配合物使烯烃的光氧化还原磷甲基化/环化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-09 DOI: 10.1039/d6qo00468g

Yang Zheng, Jiayao Zheng, Wenxue Zhao, Kai Yang, Qingqing Chen, Xiaohui Wang, Jiahui Jia, Cong Du, Chenxu Wei, Fei Chen, Xiaobo Pan

引用次数: 0

Intramolecular through-space heavy-atom effect in multiresonant thermally activated delayed fluorescence emitters with [2.2]paracyclophane 含[2.2]副环环烷的多共振热激活延迟荧光发射器的分子内穿透空间重原子效应

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-13 DOI: 10.1039/d6qo00318d

Yan Xu, Hassan Hafeez, Wenrui Wang, Ifor D. W. Samuel, Eli Zysman-Colman

{"title":"Intramolecular through-space heavy-atom effect in multiresonant thermally activated delayed fluorescence emitters with [2.2]paracyclophane","authors":"Yan Xu, Hassan Hafeez, Wenrui Wang, Ifor D. W. Samuel, 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-ortho (po) or pseudo-meta (pm) positions relative to the MR-TADF core, and were obtained. The two emitters have nearly identical emission spectra to the reference , yet exhibit faster kRISC: 5.3 × 104 s−1 (po) and 4.1 × 104 s−1 (pm) compared to 2.8 × 104 s−1 (). Despite this improvement in kRISC, the corresponding OLEDs showed no alleviation in efficiency roll-off and lower maximum external quantum efficiency (EQEmax). These findings suggest that a through-space HAE using a PCP is an effective strategy to accelerate kRISC while largely preserving spectral purity; however, this improvement in kRISC 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}

引用次数: 0

Electrochemically driven nickel catalysis for formal C–H amination 电化学驱动镍催化正态碳-氢胺化

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2026-07-01 Epub Date: 2026-05-16 DOI: 10.1039/d6qo00461j

Gege Jiang, Yun Sa, Bingnan Wang, Duanyang Kong

{"title":"Electrochemically driven nickel catalysis for formal C–H amination","authors":"Gege Jiang, Yun Sa, Bingnan Wang, 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}

引用次数: 0