Organic Chemistry Frontiers最新文献

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

Synthesis of Highly Polysubstituted Cyclopentadienes through Oxypalladation Initiated Domino Heck Reactions of Internal Alkynes 内炔氧包合引发的多米诺Heck反应合成高多取代环戊二烯

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-02 DOI: 10.1039/d5qo01231g

Zhang-Wei Liu, Jie Zhao, Yu Zhao, Yu-Feng Liang, Zhi-Xin Wang, Gui-Fa Su, Dong-Liang Mo

引用次数: 0

Unraveling Steric and Dispersion Effects in Gold Catalysis: A DFT Study of Asymmetric Cyclization/Mannich Reactions 金催化中的立体和分散效应：不对称环化/曼尼希反应的DFT研究

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-01 DOI: 10.1039/d5qo01230a

YunHe Li, Rui Jin, Ke Chu, Jin Mei Qian, Ruiyu Liu

{"title":"Unraveling Steric and Dispersion Effects in Gold Catalysis: A DFT Study of Asymmetric Cyclization/Mannich Reactions","authors":"YunHe Li, Rui Jin, Ke Chu, Jin Mei Qian, Ruiyu Liu","doi":"10.1039/d5qo01230a","DOIUrl":"https://doi.org/10.1039/d5qo01230a","url":null,"abstract":"The cooperative catalysis between gold complexes and chiral phosphoric acids (CPA) enables asymmetric oxidative cyclization/Mannich reactions of homopropargyl amides, providing efficient access to chiral spiroindolenines with high enantioselectivity. However, the mechanistic details, particularly the origin of stereocontrol governed by the interplay of steric and dispersion effects, remain elusive. Herein, we present a comprehensive density functional theory (DFT) study to unravel the reaction mechanism and the decisive factors controlling enantioselectivity. Our computations reveal that the catalytic cycle proceeds through gold-carbene formation, regioselective N-H insertion, enolization, and the stereodetermining Mannich addition. The enantioselectivity is primarily dictated by the Mannich step, wherein the favored transition state (TS-SR) is stabilized by a synergistic network of noncovalent interactions, including hydrogen bonding and dispersion forces between the sulfonamide group and the CPA catalyst. Quantitative distortion-interaction analysis demonstrates that dispersion interactions contribute significantly (~3.0 kcal/mol) to the energy difference between diastereomeric transition states. This study not only clarifies the stereochemical model but also provides a rational basis for future catalyst design in gold/CPA cooperative catalysis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203646","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

An IEDDA Reaction of Propargyl Sulfonium Salts and Tetrazines： A Versatile [4+2] Modular Assembly 丙炔磺酸盐和四嗪的IEDDA反应：一个通用的[4+2]模块组装

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-10-01 DOI: 10.1039/d5qo01092f

Jiaan Shao, Zheng Wang, Qi Zhu, Jiankang Zhang, Huajian Zhu, Wenteng Chen

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Synthesis of sulfilimines via electron donor−acceptor complexes 电子供体-受体配合物合成亚胺类化合物

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-09-30 DOI: 10.1039/d5qo01017a

Wu Ke, Junliang Zhang, Junfeng Yang

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Diels-Alder Reaction of Substituted Cyclopentadienones with Benzothiophene S, S-dioxides: Synthesis of Dibenzothiophenes, Dibenzothiophene S, S-dioxides, Acenaphthenes, Phenanthrenes, Pyrenes, and Fluorenones by Exploiting Thermolysis of Diels-Alder Adducts 取代环戊二烯酮与苯并噻吩S、S-二氧化物的Diels-Alder反应：利用Diels-Alder加合物热裂解合成二苯并噻吩、二苯并噻吩S、S-二氧化物、苊、菲、芘和芴酮

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-09-30 DOI: 10.1039/d5qo00797f

Divya Bharathi K, MANIKANDAN Palani, Arasambattu K Mohanakrishnan

{"title":"Diels-Alder Reaction of Substituted Cyclopentadienones with Benzothiophene S, S-dioxides: Synthesis of Dibenzothiophenes, Dibenzothiophene S, S-dioxides, Acenaphthenes, Phenanthrenes, Pyrenes, and Fluorenones by Exploiting Thermolysis of Diels-Alder Adducts","authors":"Divya Bharathi K, MANIKANDAN Palani, Arasambattu K Mohanakrishnan","doi":"10.1039/d5qo00797f","DOIUrl":"https://doi.org/10.1039/d5qo00797f","url":null,"abstract":"Diels-Alder (DA) reaction of a series of tetra substituted cyclopentadienones (CPDs) with benzo[b]thiophene S, S-dioxide analogues in various solvents at different temperatures led to the formation carbocyclic as well as heterocyclic compounds. The intermediate Diels-Alder adducts underwent CO extrusion followed by different aromatization patterns depending upon the nature substituents on dienes as well as dienophiles, and temperature to afford these compounds. While at temperature <150 oC, the adducts mostly furnished annulated benzo[b]thiophenes involving 1,3-H shifts followed by deoxygenation or afforded substituted arenes through SO2 extrusion. However, at an elevated temperature (>200 oC), the intermediate dihydro dibenzothiophene S, S-dioxides underwent an exclusive SO2 elimination pathway followed by an intramolecular cyclization to furnish aryl-/hetero-aryl fused phenanthrene and pyrene derivatives. Relatively, the Diels-Alder reaction of phenanthrene as well as pyrene fused CPDs required high temperature for CO and SO2 extrusions accompanied by annulation to give the corresponding π-conjugated arenes as well as hetero-arenes. The DA reaction of CPDs could also be performed with 2-indenone as a dienophile to assemble unsymmetrical fluorenones via CO extrusion followed by 1,3-H shift and subsequent oxidation of the resulting fluorenols. Alternatively, the DA reaction of acenaphthene based CPD containing electron withdrawing ester units at 7, 9-positions could be carried out with benzo[b]thiophene S, S-dioxides in nitrobenzene at reflux to afford the respective fluorenones involving SO2 extrusion followed by intramolecular anionic cyclization with an ester unit.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"78 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189229","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

Nickel-Catalyzed Synthesis of Aryl Ketones from Arylsulfonium Salts and Nitriles 镍催化芳基磺酸盐和腈合成芳基酮

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-09-30 DOI: 10.1039/d5qo01173f

Ping Wu, Guan-Sheng Jiao, Cheng-Pan Zhang

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Selectfluor-Promoted Electrophilic Aromatic Halogenation: A General Strategy for Iodination and Bromination via Oxidative Halide Activation 选择氟促进亲电芳香卤化：通过氧化卤化物活化碘化和溴化的一般策略

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-09-29 DOI: 10.1039/d5qo01114k

Fan Wu, Yuying Weng, Xubing Hu, Feng Ni

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Facile Access to Indolo[2,3-b]quinoline Alkaloids via DMSO-Mediated Cascade Cyclization: Unveiling Their Photophysical Potential 通过二甲基亚砜介导的级联环化制备吲哚[2,3-b]喹啉生物碱：揭示其光物理潜力

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-09-29 DOI: 10.1039/d5qo01193k

Gokulprasanth Nataraj, Ranjithkumar Chandran, Muniappan Kalipriyadharshini, Diksha Bansal, Easwaramoorthi Shanmugam, Mrinal Kanti Das, Saikat Chaudhuri

{"title":"Facile Access to Indolo[2,3-b]quinoline Alkaloids via DMSO-Mediated Cascade Cyclization: Unveiling Their Photophysical Potential","authors":"Gokulprasanth Nataraj, Ranjithkumar Chandran, Muniappan Kalipriyadharshini, Diksha Bansal, Easwaramoorthi Shanmugam, Mrinal Kanti Das, Saikat Chaudhuri","doi":"10.1039/d5qo01193k","DOIUrl":"https://doi.org/10.1039/d5qo01193k","url":null,"abstract":"A streamlined and efficient synthetic strategy has been established for the construction of Indolo[2,3-b]quinolines, utilizing C3-alkylated indole as the starting material and mediated by DMSO and HCl. This methodology enables the direct annulation of the quinoline ring onto a pre-functionalized indole core with high functional group compatibility. The reaction proceeds smoothly across a diverse range of substrates, delivering the desired products in consistently high yields. Its operational simplicity, scalability, and broad substrate scope highlight its practical utility, particularly for large-scale synthesis. Notably, this approach provides a valuable platform for the synthesis of complex natural products featuring the Indolo[2,3-b]quinoline framework. Indolo[2,3-b]quinolines show strong blue to blue-green fluorescence with large Stokes shifts due to excited-state proton transfer. Substituents on the pyrrolic nitrogen and aromatic core significantly affect absorption and emission by altering hydrogen bonding and photobasicity. Electron-donating groups at the 5-position increase fluorescence lifetime and quantum yield.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145183374","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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New mode of sulfur ylides reactivity: stereoelectronic control provides C–C bond insertion before cyclopropanation/epoxidation directly affording homologated three-membered rings 硫酰化物反应的新模式：立体电子控制在环丙烷化/环氧化之前提供C-C键插入，直接提供同构的三元环

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-09-29 DOI: 10.1039/d5qo01266j

Vitaly Shorokhov, Beauty K. Chabuka, Albina A Nikolaeva, Sergey S. Zhokhov, Ivan A. Andreev, Nina K. Ratmanova, Igor V. Trushkov, Olga Alexandrovna Ivanova, Igor Alabugin

引用次数: 0