Organic Chemistry Frontiers最新文献

DABCO-promoted reaction sequence of β-nitro alcohols and α-oxoaldehydes: construction of diverse tetrahydrofurans and total synthesis of (+)-bruguierol B dabco促进β-硝基醇和α-氧醛的反应序列：不同四氢呋喃的构建和(+)-bruguierol B的全合成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-09 DOI: 10.1039/d5qo01330e

Yu-Xia Lu, Xue-Jiao Lv, Yankai Liu

引用次数: 0

Photoswitchable Anion Recognition via Synergy between Chalcogen Bonding and Hydrogen Bonding 通过碳键和氢键的协同作用实现的可光敏阴离子识别

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-08 DOI: 10.1039/d5qo01341k

Rao Qin Hua, Hebo Ye, Peng He, Lei You

{"title":"Photoswitchable Anion Recognition via Synergy between Chalcogen Bonding and Hydrogen Bonding","authors":"Rao Qin Hua, Hebo Ye, Peng He, Lei You","doi":"10.1039/d5qo01341k","DOIUrl":"https://doi.org/10.1039/d5qo01341k","url":null,"abstract":"Exploring photoresponsive noncovalent interactions with controllable tunability is of great significance for advancing supramolecular recognition and smart dynamic materials. Herein, we report light-responsive hydrazone-based receptors incorporating a telluroazole-derived chalcogen bond donor for photoswitchable anion binding. The system undergoes bidirectional E/Z photoisomerization, which modulates an intramolecular NH···N hydrogen bond and hence enhances the electrophilicity of the tellurium center in Z-isomer for chalcogen bonding. This structural change enables significant increase in the binding affinity of Z-isomer toward halide anions (Cl⁻, Br⁻, I⁻), with binding constants up to 20 times higher than E-isomer. The incorporation of electron-withdrawing substituents amplifies the polarization, allowing the control over binding strength and selectivity. Moreover, anion binding facilitates Z→E photoisomerization, offering a feedback mechanism between recognition and structural switching. The study shown here demonstrates a new strategy combining reversible photochemical control and synergistic noncovalent interactions modulation, offering an effective approach for the development of stimuli-responsive supramolecular systems.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"105 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241609","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}

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Chalcogen functionalized pyrimidine synthesis by three-component free radical chalcogenation and pyrimidine ring construction 用三组分自由基加硫和嘧啶环构造法合成硫基功能化嘧啶

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-08 DOI: 10.1039/d5qo01206f

Jingfeng Ye, Gengxin Li, Changfeng Wan, Jie-Ping Wan

引用次数: 0

Сross-dehydrogenative C-O coupling of oximes with hydrazones: synthesis of fungicidal azo oxime ethers Сross-dehydrogenative氧肟与腙的C-O偶联：杀真菌偶氮氧肟醚的合成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-07 DOI: 10.1039/d5qo01151e

Alexander Budnikov, Mikhail I. Shevchenko, Igor Krylov, Daniil Y. Pechen, Anna L. Alekseenko, Alexey Ilovaisky, Alexander Olegovich Terent'ev

{"title":"Сross-dehydrogenative C-O coupling of oximes with hydrazones: synthesis of fungicidal azo oxime ethers","authors":"Alexander Budnikov, Mikhail I. Shevchenko, Igor Krylov, Daniil Y. Pechen, Anna L. Alekseenko, Alexey Ilovaisky, Alexander Olegovich Terent'ev","doi":"10.1039/d5qo01151e","DOIUrl":"https://doi.org/10.1039/d5qo01151e","url":null,"abstract":"The cross-dehydrogenative coupling (CDC) of oximes with hydrazones employing KMnO 4 as the oxidant was discovered.Presumably, the reaction proceeds through the selective cross-recombination of oxime and hydrazone-derived free radicals despite the fact that both of them are known to undergo self-coupling and other processes with C-C, C-O, C-N, and N-N bond formation. The proposed approach is general and applicable to a broad range of oximes and hydrazones. Previously, oxime derived radicals were mainly involved in intramolecular processes of C-O bond formation, while intermolecular processes remained rare and their scope was limited. On the other hand, radical functionalization of hydrazones was generally limited to radical addition and hydrogen substitution reactions of aldehyde hydrazones. The formation of azo compounds in the present work represents a distinctive direction for further development. The synthesized compounds exhibited pronounced fungicidal activity against a wide spectrum of phytopathogenic fungi (Venturia inaequalis, Rhizoctonia solani, Fusarium oxysporum, Fusarium moniliforme, Bipolaris sorokiniana, Sclerotinia sclerotiorum) in some cases surpassing the activity of commercial fungicides triadimefon, krezoxim-methyl, and azoxystrobin. Key factors contributing to the high fungicidal activity were identified as the presence of a small aliphatic substituent at the C-O coupling site and electronwithdrawing substituents in the oxime moiety.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"78 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235348","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}

引用次数: 0

Photoinduced regio- and stereoselective C(sp2)–H fluoromethylthiolation of enamides 光诱导区域和立体选择性C(sp2) - h氟甲基硫基化

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-07 DOI: 10.1039/d5qo01038a

Jian Han, Li-Li Zeng, Yue Zhou, Shi-Han Xu, Liang Shen, Wei Lin, Fener Chen

引用次数: 0

Sodium dithionite mediated reductive N-acetylation/formylation of nitroarenes employing DMAc/DMF as acetyl/formyl surrogates 二亚硝酸钠以DMAc/DMF作为乙酰基/甲酰代物介导硝基芳烃的n -乙酰化/甲酰化反应

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-07 DOI: 10.1039/d5qo01199j

Amitava Hazra, Komal Mendhe, Joydev K. Laha

引用次数: 0

Mechanistic Insights into NHC/Cu Catalyzed Asymmetric Synthesis of Spirooxindole: Origins of Enantioselectivity and Diastereoselectivity NHC/Cu催化不对称合成螺菌吲哚的机理：对映选择性和非对映选择性的起源

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-07 DOI: 10.1039/d5qo01235j

Lili Zhao, Qin Ma, Shuqi Zhang, Qingshuang Zhang, Xing Yang, Lei Qin

{"title":"Mechanistic Insights into NHC/Cu Catalyzed Asymmetric Synthesis of Spirooxindole: Origins of Enantioselectivity and Diastereoselectivity","authors":"Lili Zhao, Qin Ma, Shuqi Zhang, Qingshuang Zhang, Xing Yang, Lei Qin","doi":"10.1039/d5qo01235j","DOIUrl":"https://doi.org/10.1039/d5qo01235j","url":null,"abstract":"Density Functional Theory (DFT) calculations were conducted to elucidate the mechanism of NHC/Cu catalyzed enantioselective annulation between isatin-derived enals and ethynyl carbonates, enabling the asymmetric synthesis of spirooxindole δ-lactones with vicinal all-carbon quaternary stereocenters. The catalytic process involves four key stages: (i) generation of azolium homoenolate intermediate IM3 via NHC-mediated nucleophilic addition to enal 1a; (ii) [Cu]-catalyzed decarboxylation of ethynyl carbonate 2a to afford the copper-alkynyl intermediate IM7; (iii) stereoselective C-C bond formation between IM3 and IM7, followed by a two-water-mediated enol-keto tautomerization yielding the ketone intermediate IM10; and (iv) NEt3-promoted deprotonation, intramolecular cyclization, and proton transfer affording product spirooxindole δ-lactone 3a. Notably, both the enantio-and diastereoselectivity-determining step and the rate-determining step occur in Stage III. Further DIAS and QTAIM analyses of four stereoisomeric transition states identify TS5(S,R) as the most favorable, exhibiting the lowest free energy barrier and multiple stabilizing non-covalent interactions (C-H⋯π, C-H⋯O, C-F⋯π, and Cu⋯H), rationalizing the observed high stereoselectivity. Water molecules are shown to play a crucial role in lowering the barrier of the rate-determining step by enhancing electrostatic, orbital, and dispersion interactions. This study not only deepens the mechanistic understanding of cooperative NHC/Cu catalysis but also provides valuable theoretical guidance for rational designing next-generation asymmetric annulation reactions.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235351","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}

引用次数: 0

Chiral Bis-Phosphine Monoxide-Gold(I) Complex Enables Asymmetric Dearomative Cyclization of β-Naphthol Derivatives 手性双膦-一氧化二氢-金(I)配合物使β-萘酚衍生物发生不对称脱芳环化

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-03 DOI: 10.1039/d5qo01109d

Xiaoyu Liu, Ya-Ru Wan, Yumeng Yang, Runming Wang, Zili Chen

{"title":"Chiral Bis-Phosphine Monoxide-Gold(I) Complex Enables Asymmetric Dearomative Cyclization of β-Naphthol Derivatives","authors":"Xiaoyu Liu, Ya-Ru Wan, Yumeng Yang, Runming Wang, Zili Chen","doi":"10.1039/d5qo01109d","DOIUrl":"https://doi.org/10.1039/d5qo01109d","url":null,"abstract":"Chiral phosphine ligands play a pivotal role in gold(I)-catalyzed asymmetric reactions, yet their efficacy is often constrained by limited strategies for chiral induction. While traditional ligands rely primarily on steric effects, the linear geometry of Au(I) centers demands innovative ligand designs capable of synergistic interactions beyond spatial hindrance. This challenge motivates the development of ligands incorporating supplementary weakly coordinating groups to enhance enantiocontrol. We herein report four novel chiral Gold(I) complexes based on bis-phosphine monoxide ligands (BPMOs), including (R)-BINAP(O)-AuCl 3a, (R)-MeO-BiPhep(O)-AuCl 3b, (S)-SegPhos(O)-AuCl 3c and (R,R)-DuPhos(O)-AuCl 3d, derived from commercially available biphosphine ligands via mono-oxidation and Au(I)-complexation. The catalytic utility of these complexes was evaluated in the intramolecular catalytic asymmetric dearomatization (CADA) reaction of β-naphthol derivatives, among which, complex 3a [(R)-BINAP(O)-AuCl] exhibited superior performance, delivering a series of spiro-naphthalenone products in good yields with moderate to high enantiomeric excess. Experimental and computational studies reveal that the P=O moiety in 3a facilitates a critical hydrogen-bonding interaction with the substrate, synergizing with Au(I)-alkyne coordination to rigidify the transition state and amplify stereocontrol. This work establishes chiral BPMO-Au(I) complexes as versatile catalysts for asymmetric dearomatization, with demonstrated scalability and applicability to diverse β-naphthol substrates.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209715","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}

引用次数: 0

Precipitation-Driven Diastereo- and Regioselective Macrocyclization via Benzoin Condensation: Effects of Solvents and Alkyl Chain Lengths 沉淀驱动的非立体和区域选择性大环化：溶剂和烷基链长度的影响

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-03 DOI: 10.1039/d5qo01179e

Kosuke Ono, Junya Fukumoto, Yu Tanoi, Hidetoshi Kawai

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Metal-free cascade SNAr reaction/allylic amination enabled by triethylamine: a green chemistry access to tetrahydropteridines 由三乙胺实现的无金属级联SNAr反应/烯丙基胺化：四氢蝶啶的绿色化学途径

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-02 DOI: 10.1039/d5qo01211b

Bendu Pan, Yunru Wu, Liwei Zhao, Rihui Cao, Liqin Qiu

{"title":"Metal-free cascade SNAr reaction/allylic amination enabled by triethylamine: a green chemistry access to tetrahydropteridines","authors":"Bendu Pan, Yunru Wu, Liwei Zhao, Rihui Cao, Liqin Qiu","doi":"10.1039/d5qo01211b","DOIUrl":"https://doi.org/10.1039/d5qo01211b","url":null,"abstract":"Herein, we report a novel metal-free cascade SNAr reaction/allylic amination strategy for pyrimidinamine derivatives promoted by cost-effective triethylamine, enabling the efficient synthesis of a wide range of 2-chlorotetrahydropteridines in moderate to good yields under air atmosphere. This operationally simple protocol demonstrates notable advantages including one-pot synthesis and utilization of environmentally benign solvents. The obtained 2-chlorotetrahydropteridines serve as versatile synthons for constructing diverse 2-substituted tetrahydropteridine derivatives through conventional palladium-catalyzed Suzuki–coupling and Buchwald–Hartwig amination reactions using (SIPr)Ph₂Pd(cin)Cl as the N-heterocyclic carbene-palladium catalyst. Systematic mechanistic investigations, including successful isolation and monitoring of key intermediates, provide a deeper insight into the reaction pathway. The methodology's sustainability is further evidenced by successful attempts at solvent-free optimization, gram-scale production feasibility, and synthetic application of the resulting products. This green synthetic approach significantly reduces the environmental impact through eliminating the requirement for an inert atmosphere, establishing a robust platform for the sustainable synthesis of tetrahydropteridines.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203645","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}

引用次数: 0