{"title":"Copper-Catalyzed Three-Component 1,2-Aryl Sulfonylation of Vinylarenes and 1,3-Dienes with Sodium Sulfinates","authors":"Wei-Hao Rao, Chang Gao, Li-Li Jiang, Xiao-Wen Dong, Yi-Wen Li, Chen-Xi Ge, Jia Li, Mengcheng Zhang","doi":"10.1039/d5qo00993f","DOIUrl":"https://doi.org/10.1039/d5qo00993f","url":null,"abstract":"A copper-catalyzed three-component 1,2-aryl sulfonylation of vinylarenes and 1,3-dienes with sodium sulfinates is reported. The reaction proceeds at room temperature with excellent regioselectivity and stereoselectivity, providing an efficient and straightforward approach to various β,β-diaryl sulfones. Combing sodium sulfinates with copper catalytic system is essential for this transformation. Mechanistic studies reveal that sulfonyl radicals originated from sodium sulfinates undergo addition across alkenes to form new benzylic radicals that subsequently undergo copper-catalyzed arylation with aryl boronic acids.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"62 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144840266","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}
Ke Xu, Kejun Lin, Jiayi Zhao, Jingmei Zeng, Tingshun Zhu
{"title":"Atroposelective [5+5] formation of Benzo[c]chromenone and Phenanthridinone by Carbene organocatalysis","authors":"Ke Xu, Kejun Lin, Jiayi Zhao, Jingmei Zeng, Tingshun Zhu","doi":"10.1039/d5qo00986c","DOIUrl":"https://doi.org/10.1039/d5qo00986c","url":null,"abstract":"The N-heterocyclic carbene organocatalyzed δ-LUMO activation strategy was used for the atroposelective [5+5] construction of benzo[c]chromenone and phenanthridinone. The cascades involved a regioselective and stereoselective 1,6-addition, an intramolecular aldol reaction, a chemoselective lactonization, dehydration, and the successive oxidative aromatization with the simultaneously point-to-axial chirality transfer process. Axially chiral biaryls with gradient rotation barriers were synthesized and investigated. The multicyclic aromatic products can be obtained on a gram scale and further transformed into several interesting molecules. This study further expands the organocatalyzed benzannulation methods to the construction of more sophisticated multicyclic aromatics.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144825198","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 one-step C2–H methylation of free (N–H) indoles enabled by Pd(II)/norbornene cooperative catalysis","authors":"Yutong Sun, Wenlin Zhang, Ying Liu, Zhixin Zhang, Mengyao Hu, Xiaoguang Liu, Hongbo Qin, Helin Lu","doi":"10.1039/d5qo00869g","DOIUrl":"https://doi.org/10.1039/d5qo00869g","url":null,"abstract":"The C2-methylated indole scaffolds are prevalent and crucial components of numerous pharmaceutical molecules and biologically active entities. However, its synthesis traditionally requires a laborious three-step sequence involving the installation of suitable directing groups, C2-functionalization, and deprotection. Herein, we report a one-step, regioselective C2–H methylation of free (N–H) indoles via Pd(II)/norbornene(NBE) catalysis using trimethyl phosphate as a practical methyl source. This modular methodology uniquely circumvents previous multi-step strategies, demonstrating broad applicability with excellent functional group tolerance, high to quantitative yields, robust scalability, successful trideuteromethylation, and operational simplicity due to its air and moisture insensitivity. This step-economical strategy significantly streamlines access to valuable C2-methylated indole derivatives, offering a more direct and efficient pathway for late-stage methylation of drug-like indoles compared to previous methods.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144819687","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}
Alexander A. Sapronov, Olga Chusova, Alexander S Peregudov, Alexey S. Kubasov, Victor N Khrustalev, Alexander V Borisov, Zhanna V. Matsulevich, Evgeniy chipinsky, Vladimir K. Osmanov, Rosa Maria Gomila, Antonio Frontera, Valentine Nenajdenko, Alexander Tskhovrebov
{"title":"Novel Class of 1,2-Diselenazoles via Cationic Polar Cycloaddition between Ambiphilic 2-Pyridylselenyl Reagents and Isoselenocyanates Exhibiting High Antifungal Activity","authors":"Alexander A. Sapronov, Olga Chusova, Alexander S Peregudov, Alexey S. Kubasov, Victor N Khrustalev, Alexander V Borisov, Zhanna V. Matsulevich, Evgeniy chipinsky, Vladimir K. Osmanov, Rosa Maria Gomila, Antonio Frontera, Valentine Nenajdenko, Alexander Tskhovrebov","doi":"10.1039/d5qo00927h","DOIUrl":"https://doi.org/10.1039/d5qo00927h","url":null,"abstract":"We report the synthesis and structural characterization of a novel class of pyridinium-fused 1,2-diselenazoles, obtained via a regioselective cationic polar cycloaddition between ambiphilic 2-pyridylselenyl reagents and isoselenocyanates. All new compounds were isolated in high yields and fully characterized by NMR, HRMS, and single-crystal X-ray diffraction. Density functional theory calculations reveal a concerted cycloaddition mechanism, with a low activation barrier and no detectable intermediates. Molecular electrostatic potential analysis of representative diselenazolium cations highlights the presence of two prominent σ-holes per molecule, favoring strong directional chalcogen bonding with halide anions. QTAIM/NCIplot and NBO analyses confirm the noncovalent and orbital-driven nature of the Cl···Se–Se interactions, supported by significant second-order stabilization energies and short Se···Cl contacts. The antifungal activity of novel diselenazoles was evaluated against six phytopathogenic fungi. Most compounds demonstrated strong inhibition at 30 mg/L, with several derivatives exhibiting superior efficacy compared to the commercial fungicide Tebuconazole at reduced concentrations (15 and 3 mg/L). Notably, certain diselenazoles showed exceptional activity against Venturia inaequalis and Rhizoctonia solani, surpassing Tebuconazoles’ performance. The best-in-class compounds were evaluated for their effects on the seeds of higher plants. Root growth was found to be stimulated at the lowest exposure concentration of 3 mg/L for wheat, barley and cress.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144825196","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":"Ru(II)-Catalyzed Direct Alkynylation of 2-Acylimidazoles with TIPS-Alkynes or TIPS-Bromoalkynes under Air","authors":"Yuting Gui, Xingchi Li, Ting Fu, Taoyuan Liang, Zequan Li, Shuangliang Zhao, Zhuan Zhang","doi":"10.1039/d5qo00868a","DOIUrl":"https://doi.org/10.1039/d5qo00868a","url":null,"abstract":"The Ru(II)-catalyzed <em>ortho</em>-alkynylation of 2-acylimidazoles is reported, demonstrating compatibility with TIPS-protected terminal alkynes or TIPS-protected bromoalkynes as alkynylating reagents. The reaction tolerates a wide range of functional groups, and the resulting alkynylated products can be readily transformed into high-value compounds, presenting promising applications in medicinal chemistry and materials science. This strategy addresses the existing gap by proposing that the alkynylation reaction proceeds through six-membered ruthenacycle intermediates.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144819686","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}
Satenik Mkrtchyan, Gabriela Addová, Juraj Filo, Khurshid Ayub, Michael G Garcia, Spartak Spiridonovich Khutsishvili, Yevhen Karpun, Elena Kupcová, Vishal B. Purohit, Sehrish Sarfaraz, Mohanad Shkoor, Barbora Benicka, Oleksandr Shalimov, Vitaliy Yepishev, Jiří Zapletal, Viktor Iaroshenko
{"title":"Mechanochemical Production of Biphenyls from Nitrogen-Containing Organic Compounds: Amides, Anilines, and Sulfonamides","authors":"Satenik Mkrtchyan, Gabriela Addová, Juraj Filo, Khurshid Ayub, Michael G Garcia, Spartak Spiridonovich Khutsishvili, Yevhen Karpun, Elena Kupcová, Vishal B. Purohit, Sehrish Sarfaraz, Mohanad Shkoor, Barbora Benicka, Oleksandr Shalimov, Vitaliy Yepishev, Jiří Zapletal, Viktor Iaroshenko","doi":"10.1039/d5qo01041a","DOIUrl":"https://doi.org/10.1039/d5qo01041a","url":null,"abstract":"The presence of C(sp2)–NH2 in pharmaceutical building blocks provokes a pressing demand for the discovery and development of deaminative functionalization of the C(sp2)–NH2 moeity to enable new routes for late-stage functionalization of complex molecules. In this work, we disclose a mechanochemical deaminative arylation of C(sp2)–NH2 by in situ conversion of C(sp2)–NH2 to reactive pyridinium salts via selective condensation of C(sp2)–NH2 with pyrylium tetrafluoroborate. Deaminative coupling of anilines, amides, and sulfonamide represents a key development for the selective functionalization process, enabling production of precursor biphenyl compounds with the potential to develop biologically active molecules.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144819688","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}
Paula Gonzalez-Andres, Alberto Cherubin, Asuncion Barbero
{"title":"Expanding the silyl-Prins toolbox: selective access to C4-quaternary stereocenters in tetrahydropyrans using internal cyclopropylsilyl alcohols","authors":"Paula Gonzalez-Andres, Alberto Cherubin, Asuncion Barbero","doi":"10.1039/d5qo00984g","DOIUrl":"https://doi.org/10.1039/d5qo00984g","url":null,"abstract":"Our ongoing research into silyl-Prins cyclizations has now provided a promising solution for the stereoselective synthesis of tetrahydropyrans bearing quaternary centers at C4. Building on previous success with terminal cyclopropylsilyl alcohols, we now demonstrate that internal cyclopropylsilyl alcohols can also be effectively employed to construct highly substituted tetrahydropyrans. This new approach delivers products featuring both a quaternary center at C4 and a tertiary center at C6 with excellent stereocontrol. These findings not only broaden the scope of silyl-Prins cyclization but also establish a general and efficient strategy for accessing complex oxacyclic architectures with precise stereochemical outcomes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144813053","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 Phenanthridines via Palladium-Catalyzed Annulation of 2-Iodobenzimines with 2-Halobenzoic Acids","authors":"Ying Fu, Hao Chen, Yu Luo, Wenying Yang, Liying Jia, Zhengyin Du","doi":"10.1039/d5qo00968e","DOIUrl":"https://doi.org/10.1039/d5qo00968e","url":null,"abstract":"A palladium-catalyzed decarboxylative annulation reaction of 2-iodobenzimines with 2-halobenzoic acids for the synthesis of phenanthridine scaffolds has been developed. Density functional theory calculations revealed that in the presence of the KOAc additive, this annulation reaction proceeds via Pd(II) transmetalation pathway rather than the oxidative Pd(IV) formation pathway. The base Cs2CO3 plays a crucial role in C−H bond activation, which is the rate-determining step.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144802930","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}
Weikang Li, Zhe Chen, Chuanyi Xiong, Zhenjie Yang, Ning Wang, Peifeng Su, Yaru Jing, Haihua Huang, Zhuofeng Ke
{"title":"Catalyst-Free Reductive Desulfurization of Thioamides with Ammonia Borane through Concerted Double-hydrogen Transfer Mechanism","authors":"Weikang Li, Zhe Chen, Chuanyi Xiong, Zhenjie Yang, Ning Wang, Peifeng Su, Yaru Jing, Haihua Huang, Zhuofeng Ke","doi":"10.1039/d5qo01028d","DOIUrl":"https://doi.org/10.1039/d5qo01028d","url":null,"abstract":"The green reductive transformation of thioamides is highly desired yet faces challenges in broad substrate scope and selectivity for C=S and C-N cleavage. Existing catalytic hydrogenation methods are still limited and require harsh reaction conditions. Here, a computation-aided design discovered a catalyst-free protocol for thioamides’ reductive desulfurization with ammonia borane (AB). The system uses dimethylamine borane (DMAB) to directly reduce thioamides to amines under catalyst-free, practical, economical, green, and easy-to-handle conditions. It covers a broad scope for primary, secondary, and tertiary thioamides. The experimental and theoretical studies revealed a concerted double-hydrogen transfer mechanism for this catalyst-free system, in which DMAB was found an important self-catalysis role in the reaction. This practical and selective protocol could provide an important example for designing catalyst-free reductive systems.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"78 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792404","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}
Satenik Mkrtchyan, Oleksandr Shalimov, Michael G. Garcia, Gabriela Addová, Juraj Filo, Sehrish Sarfaraz, Khurshid Ayub, Vishal B. Purohit, Viktor O. Iaroshenko
{"title":"One-pot Mo(CO)6-facilitated transformation of anilines into benzophenones via in situ pyridinium reconfiguration","authors":"Satenik Mkrtchyan, Oleksandr Shalimov, Michael G. Garcia, Gabriela Addová, Juraj Filo, Sehrish Sarfaraz, Khurshid Ayub, Vishal B. Purohit, Viktor O. Iaroshenko","doi":"10.1039/d5qo00920k","DOIUrl":"https://doi.org/10.1039/d5qo00920k","url":null,"abstract":"A novel, mechanochemical, one-pot transformation of anilines to benzophenones using molybdenum hexacarbonyl (Mo(CO)<small><sub>6</sub></small>) was achieved, avoiding pre-functionalization steps inherent in such conversions. The reaction capitalizes on the activation of the C(sp<small><sup>2</sup></small>)–NH<small><sub>2</sub></small> bond in anilines <em>via in situ</em> formation of pyridinium salts: a strategy impeded by the inertness of the C–N bond. For this envisioned methodology, pyrylium tetrafluoroborate was used to convert anilines into reactive pyridinium intermediates, which undergo carbonylation in the presence of Mo(CO)<small><sub>6</sub></small>. The corresponding acyl pyridinium intermediates, in turn, are amenable for C–C coupling under transition metal catalyst-free conditions, driven by the piezoelectric nature of barium titanate in a mechanochemical reaction setup. This approach shows a very general substrate scope, good functional group tolerance, and fair-to-excellent yields (50–92%, depending on the aniline derivative used) of benzophenone analogues. This acyl-intermediate-based method has been further applied to the synthesis of 3-benzoylchromones, attesting to its broad scope. Therefore, the described late-stage functionalization strategy, free of transition metals, represents progress in the scope of bioactive compound syntheses for medicinal chemistry.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144792405","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}