Organic Chemistry Frontiers最新文献

{"title":"N-confused oxahexaphyrin: oxidative furan ring-opening and fusion triggered chirality","authors":"Gaojie Zhu, Zimei Ma, Che Yang, Feng Sha, Glib Baryshnikov, Bin Zhu, Mingbo Zhou, Chengjie Li, Hans Ågren, Jianxin Song, Shijun Li, Qizhao Li, Yongshu Xie","doi":"10.1039/d5qo01104c","DOIUrl":"https://doi.org/10.1039/d5qo01104c","url":null,"abstract":"Oxidative ring-closure of N-confused hexapyrrane and thiahexapyrrane followed by oxidative opening of the pyrrole and thiophene rings has been shown to be effective in synthesizing novel porphyrinoids. In this work, a furan unit is incorporated with the purpose to generate a C=O double bond by oxidative furan ring-opening to disrupt the conjugation, resulting in structural distortion and chirality. Thus, a nonaromatic N-confused oxahexaphyrin (<strong>1</strong>) has been synthesized by the oxidative cyclization of N-confused oxahexapyrrane (<strong>N-O-P<small>₅</small></strong>) with terminal confused pyrrole and furan units. Subsequent heating of <strong>1</strong> in MeOH triggered furan-opening and fusion reactions to give globally nonaromatic porphyrinoids <strong>2</strong> and <strong>3</strong> that both contain a carbonyl group and a multiply fused fragment. Thus, <strong>2</strong> possesses a [6.5.6.5]-tetracyclic fragment involving an <em>sp</em><small>³</small>-C. In contrast, one tetrafluorophenyl unit is generated in <strong>3</strong> by fusion one of the meso-C<small>₆</small>F<small>₅</small> groups with a furan-generated carbon through removing one HF unit, leading to the formation of a fused [5.6.5.7.6]-pentacyclic fragment. As expected, the C=O double bond present in the frameworks of <strong>2</strong> and <strong>3</strong> results in disrupted conjugation and structural distortion, and the fused rings are favorable for enhancing the stability of the distorted conformations, which enables chiral separation of enantiomers of <strong>2</strong> with central chirality and <strong>3</strong> with planar chirality via chiral high-performance liquid chromatography, with the maximum absorption dissymmetry factor (|g<small>_abs</small>|) of 0.0021 observed for <strong>2</strong>. This work provides insight into developing chiral porphyrinoids by post-synthetic methods based on the combination of a highly reactive N-confused pyrrole unit with a terminal furan ring.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"35 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of non-symmetric ortho-functionalized azoarenes through arylation of arylazo sulfones","authors":"Rayhane Hammami, Victor Flon, Morgane Sanselme, Julien Legros, Isabelle Chataigner, Laetitia Chausset Boissarie","doi":"10.1039/d5qo00932d","DOIUrl":"https://doi.org/10.1039/d5qo00932d","url":null,"abstract":"A novel protocol for the arylation of arylazo sulfones with organomagnesiums for accessing non-symmetric ortho-functionalized azoarenes has been succesfully developped. Bench-stable substituted arylazo sulfones, which serve as masked electrophilic diazo sources, have been effectively arylated, achieving good to excellent isolated yields. This method demonstrates broad tolerance towards a wide variety of substituents. Further, the mechanism and the regioselectivity of the addition has been investigated using DFT calculations. The observed regioselectivity would arise from a combination of steric and electronic effects, as well as the presence or absence of a strongly coordinating substituent at the ortho position of the arylazo sulfone.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"76 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Monodentate Halogen Bond Activation of Aziridines in Formal [3+2] Cycloadditions","authors":"Mattis Damrath, Boris Johannes Nachtsheim","doi":"10.1039/d5qo01119a","DOIUrl":"https://doi.org/10.1039/d5qo01119a","url":null,"abstract":"The ring opening of aziridines to produce various N-heterocycles traditionally requires strong Lewis acids or transition metal catalysts, with non-covalent organocatalytic approaches remaining largely unexplored. Herein, we demonstrate that Nheterocyclic iodonium salts can effectively catalyze [3+2] cycloadditions of aziridines through a monodentate halogen bond (XB) activation. Using 1-5 mol% of the iodolium catalyst, a wide range of aziridines undergo an efficient cycloaddition with a variety of dipolarophiles (carbonyls, alkynes, and alkenes) to furnish oxazolidines, pyrrolines, and pyrrolidines. DFT calculations revealed a previously underexplored N-activation mode, with detailed non-covalent interaction analysis showing that the N-heterocyclic iodonium salt's exceptional performance stems from combined I-N and I-π interactions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nitrosobenzenes as a stepping stone for the development of transition metal and metal-free organic transformations: a comprehensive review","authors":"Nandini R., Ramesh B. Dateer","doi":"10.1039/d5qo00842e","DOIUrl":"https://doi.org/10.1039/d5qo00842e","url":null,"abstract":"Over the past few years, there has been exponential progress in the synthesis of value-added molecules utilizing nitroso compounds. The reactions of nitroso compounds with economically cheap reactive precursors have drawn much interest from organic chemists across the globe due to their high regioselectivities; enantioselectivities; and efficiencies for annulation, C–H activations, cycloaddition, Diels–Alder reaction, and notable metal-free reactions. In particular, the nitroso moiety has recently emerged as a powerful synthon and transformable directing group in direct C–H functionalization reactions. In this review, we have broadly discussed recent reports on the versatile applications of nitroso compounds as useful building blocks in the selective synthesis of a diverse range of molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145077872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rhodium-Catalyzed Cycloaddition of Bicyclo[1.1.0]butanes with N,N’-Cyclic Azomethine Imines: En Route to Fused Diaza-3D Scaffolds","authors":"Tianlei Du, Qiujie Qin, Jin Li, Yuting Shen, Zixi Wang, Kun Yin, Xinyao Li, Jian Li, Zijun Zhou","doi":"10.1039/d5qo01147g","DOIUrl":"https://doi.org/10.1039/d5qo01147g","url":null,"abstract":"The construction of aza-3D frameworks has emerged as a pivotal strategy in drug discovery, owing to their ability to mimic heteroarene bioisosteres. In this study, we introduce a novel strategy that employs an octahedral rhodium complex as an efficient Lewis acid catalyst for the cycloaddition reaction between bicyclo[1.1.0]butanes and N,N’-cyclic azomethine imines, yielding versatile azabicyclo[3.1.1]heptane derivatives. The reaction proceeds smoothly with a broad substrate scope, achieving yields of up to 98% in 27 examples. The synthetic feasibility of this cycloaddition reaction was demonstrated through a scaled-up reaction using only 2 mol% catalyst loading, followed by further transformations of the cyclized BCHeps product. Control experiment together with DFT caculations illustrated the detailed reaction pathway. Additionally, we have developed an enantioselective version of this reaction using a chiral-at-Rhodium catalyst (up to 91% ee).","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"122 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Gold-catalyzed azidation with TMSN3 and mechanistic studies","authors":"Jiawen Wu, Siying Zhao, Xiu-Tian-Feng E, Junfeng Wang, Zhonghua Xia","doi":"10.1039/d5qo01091h","DOIUrl":"https://doi.org/10.1039/d5qo01091h","url":null,"abstract":"The growing demand for aryl azides in diverse fields has spurred significant advances in their synthetic methodologies. Herein, we report a gold-catalyzed C–N₃ cross-coupling reaction enabled by ligand-supported Au(I)/Au(III) redox catalysis. This method employs trimethylsilyl azide (TMSN₃) as a practical azide source to efficiently convert simple aryl iodides into the corresponding aryl azides. Key features of this transformation include broad substrate scope and compatibility with post-functionalization strategies. Mechanistic insights derived from combined experimental studies, computational analyses, and X-ray crystallography of two key intermediates reveal that oxidative addition and ligand exchange/azide transfer proceed smoothly, whereas thermal or photoinduced conditions facilitate the challenging reductive elimination of the Au(III)–azide intermediate.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145067780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nucleophilic addition of sulfoxonium ylides to hypervalent iodine diazo compounds as N-terminal electrophiles: direct access to novel functionalized hydrazones","authors":"Varun Anand, Ruchir Kant, Namrata Rastogi","doi":"10.1039/d5qo00885a","DOIUrl":"https://doi.org/10.1039/d5qo00885a","url":null,"abstract":"A catalyst and additive-free nucleophilic addition of sulfoxonium ylides to hypervalent iodine diazo reagents as N-terminal electrophiles has been developed. The reaction not only leads to a facile access to highly functionalized hydrazones but also significantly advances the understanding of hitherto unexplored terminal <em>N</em>-electrophilicity in HIDCs. The operational simplicity, wide substrate scope, high product yields and mild conditions are notable features of the methodology.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"89 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Alkyne-Inserted Tetraphenylethylene Derivatives: Enhanced Aggregation-Induced Emission via Intramolecular and Intermolecular Interactions","authors":"Yi-Yun Zhu, Wenhao Li, Yan-Qi Fan, Hao-Chen Lu, Donghui Wei, Xuenian Chen","doi":"10.1039/d5qo01158b","DOIUrl":"https://doi.org/10.1039/d5qo01158b","url":null,"abstract":"Solid-state luminescence is often hindered by aggregation-caused quenching (ACQ), prompting the search for efficient aggregation-induced emission (AIE) materials. Tetraphenylethylene (TPE), a star molecule in AIE research, has been widely used to study the restricted intramolecular motion (RIM) mechanism through structural modifications. Breaking from traditional peripheral modification, we engineer the TPE core by inserting an alkynyl linker between the triphenylethylene (TriPE) core and planar chromophores (TriPE-yn-Ar), where the alkynyl bond length and spatial orientation dictate molecular conformations, intermolecular interactions, and crystal packing, as well as the torsional oscillation along the rotation axis. The TriPE-yn-9-Phen demonstrates J-aggregation-enhanced emission with quantum yields of 69.9% in solid and 88.4% in crystal, with an AIE factor of 221. This central modification strategy opens new avenues for designing advanced AIE materials.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Regioselective Formation of Naphtho[2,1-b]selenophenes via Cascade Cyclization of 1,3-Diynylpropargyl Alcohols Promoted by Iron(III) Chloride and Diorganyl Diselenides","authors":"Pedro Pauletto, Davi Back, Cristina Nogueira, Gilson Zeni","doi":"10.1039/d5qo01195g","DOIUrl":"https://doi.org/10.1039/d5qo01195g","url":null,"abstract":"This manuscript reports a selective diorganyl diselenide/iron(III)-promoted strategy for the synthesis of selenium-containing heterocycles, specifically naphtho[2,1-b]selenophene derivatives, via cascade cyclization reactions.Using 1,3diynylpropargyl alcohols as key substrates and diorganyl diselenides as selenium sources, the optimized conditions involve iron(III) chloride and dibutyl diselenide in dichloromethane under an inert atmosphere at room temperature, followed by the addition of the substrate and stirring for 12 hours. A series of 25 novel derivatives was synthesized in good yields, demonstrating the scope and versatility of the protocol, which was also extended to include diorganyl disulfides. However, the optimized conditions did not work for diorganyl ditellurides, even when some reaction parameters were changed. The reaction mechanism insights are discussed, and the synthetic utility of the resulting heterocycles as intermediates in further transformations is showcased. This cascade process enables the formation of four new bonds (carbon-carbon, carbonselenium, selenium-carbon, and carbon-selenium) in a single reaction step.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"66 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic and Machine Learning Insights into Borrowing Hydrogen Reactions Catalyzed by Transition Metal Complexes with N-Heterocyclic Ligands","authors":"Hui-Qi Mo, Cheng Hou","doi":"10.1039/d5qo01139f","DOIUrl":"https://doi.org/10.1039/d5qo01139f","url":null,"abstract":"Pyrazole-based transition metal complexes have attracted increasing attention in borrowing hydrogen (BH) reactions, particularly when employing the metal–ligand cooperation (MLC) strategy to achieve high activity and selectivity. However, a systematic understanding of their mechanistic selectivity and the factors governing catalytic performance remains lacking. Herein, the BH reaction of alcohols catalyzed by such complexes was investigated using density functional theory (DFT) calculations in combination with machine learning (ML) methods. Three possible pathways—N₂-site-assisted, O-site-assisted, and N₁-site-assisted—were proposed, among which the N₂-site-assisted route was identified as the most favorable. Both the dehydrogenation and hydrogenation steps proceed via an outer-sphere concerted transfer mechanism. Distortion/interaction analysis revealed that the ligand-assisted distortion energy plays a decisive role in determining the activation barrier. Furthermore, an ML model with high predictive accuracy (R² = 0.96) was established to correlate catalytic performance with electronic and steric descriptors. Feature importance analysis identified the HOMO energy level, dipole moment, and molecular volume as key factors, reflecting the roles of electron-donating ability, transition-state polarization, and steric effects, respectively. This study not only deepens the mechanistic understanding of MLC-enabled BH reactions catalyzed by pyrazole-based transition metal complexes but also provides a predictive framework for the rational design of efficient and tunable catalysts.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145059784","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}