Organic Chemistry Frontiers最新文献_第3页

Construction of Spiro Annulated N-Centered Peri-Fused Cycles (NCPCs) via Rh(III)-Catalyzed Regioselective C-5(H) Activation of Imidazo[1,2-a]pyridine 通过Rh（III）催化区域选择性C-5(H)活化咪唑[1,2-a]吡啶构建螺旋环n中心近熔环(ncpc

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-04 DOI: 10.1039/d6qo01384h

Mehak Sood,Krishanu Debnath,Prasad V. Bharatam

{"title":"Construction of Spiro Annulated N-Centered Peri-Fused Cycles (NCPCs) via Rh(III)-Catalyzed Regioselective C-5(H) Activation of Imidazo[1,2-a]pyridine","authors":"Mehak Sood,Krishanu Debnath,Prasad V. Bharatam","doi":"10.1039/d6qo01384h","DOIUrl":"https://doi.org/10.1039/d6qo01384h","url":null,"abstract":"Selective peri-C-H functionalization with weakly coordinating directing groups remains a long standing challenge because of the intrinsic preference for competing ortho activation. Herein, we report a Rh(III)-catalyzed, carboxamidedirected, carbene-mediated [5+1] annulation that overcomes this selectivity barrier, enabling regioselective activation of the peri-C-5(H) bond of imidazo [1,2-a]pyridines. This transformation proceeds with complete site selectivity, affording exclusive C-5 annulation even in the presence of the inherently more reactive C-2(H) bond. This strategy provides rapid access to an unprecedented class of spiro-annulated N-centered peri-fused cycles (NCPCs), integrating peri-fused and spirocyclic architectures within a single molecular framework having central N-atom. The protocol exhibits broad substrate scope, is readily scalable, and enables post-functionalization. Mechanistic studies, including control experiments and DFT calculations, reveal that carbene insertion preserves the energetically favored peri-cyclometalated intermediate, thereby overriding the conventional preference for ortho annulation. This work establishes a general approach to architecturally sophisticated NCPC scaffolds through challenging peri-C-H bond functionalization.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149359406","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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Rapid and Modular P=N Bond Formation through Photoredox Radical Convergence 通过光氧化还原自由基收敛快速和模块化P=N键形成

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-04 DOI: 10.1039/d6qo01358a

Ranran Chen,Linbin Yao,Shiwei Lü,Jian Yang,Bencan Tang,Min Zhang,Zhenda Tan

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Multicomponent synthesis and photophysical properties of fluorescent amino-substituted iminoboronate (AMIBO) dyes 氨基取代亚氨基硼酸盐荧光染料的多组分合成及其光物理性质

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-03 DOI: 10.1039/d6qo01285j

Jesús Aguilar-Morgado,Joanna Olesiak-Bańska,Robert Zaleśny,Abel Ros,Uwe Pischel

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Competition between Charge and Orbital Control Governs the Divergent Reactivity of Hydrazines toward Donor-Acceptor Cyclopropanes 电荷控制和轨道控制之间的竞争决定了肼对供体-受体环丙烷的不同反应性

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-03 DOI: 10.1039/d6qo01409g

Kanstantsin V. Anisovich,Ernal R. Gaiazov,Beauty K. Chabuka,Maksim A. Boichenko,Danila S. Lebedev,Elena A. Tarasenko,Andrey Yu. Plodukhin,Sergey S. Zhokhov,Nina K. Ratmanova,Ivan A. Andreev,Igor V. Trushkov,Igor V Alabugin,Olga Alexandrovna Ivanova

{"title":"Competition between Charge and Orbital Control Governs the Divergent Reactivity of Hydrazines toward Donor-Acceptor Cyclopropanes","authors":"Kanstantsin V. Anisovich,Ernal R. Gaiazov,Beauty K. Chabuka,Maksim A. Boichenko,Danila S. Lebedev,Elena A. Tarasenko,Andrey Yu. Plodukhin,Sergey S. Zhokhov,Nina K. Ratmanova,Ivan A. Andreev,Igor V. Trushkov,Igor V Alabugin,Olga Alexandrovna Ivanova","doi":"10.1039/d6qo01409g","DOIUrl":"https://doi.org/10.1039/d6qo01409g","url":null,"abstract":"A reagent-controlled, chemodivergent approach to hexahydropyridazin-3-ones and 1-aminopyrrolidin-2-ones has been developed via Lewis acid-promoted ring-opening/ring-closure reactions of donor-acceptor cyclopropanes with unsymmetrically substituted hydrazines. The method enables efficient, single-step access to two classes of biologically relevant azaheterocycles in good yields under mild conditions. The reaction outcome is dictated by the nature of the hydrazine substituent: arylhydrazines bearing electron-rich or neutral groups selectively form six-membered products via internal nitrogen attack, whereas electron-withdrawing aryl substituents, acyl hydrazines, and carbazates favor fivemembered ring formation through terminal nitrogen reactivity. Both pathways proceed through a domino sequence involving nucleophilic ring opening followed by in situ Lewis acid-induced cyclization, providing a modular platform for the synthesis of structurally diverse nitrogen heterocycles. Mechanistic studies reveal that the observed selectivity arises from a competition between charge control and frontier orbital control in ambident hydrazines. While charge distribution favors the attack by the terminal nitrogen, the higher-energy lone pair on the internal nitrogen governs reactivity in arylhydrazines, leading to an inverse α-effect. This interplay, supported by stereochemical probes, NBO analysis, and computations, provides a predictive framework for the ambident reactivity of hydrazines in reactions with activated cyclopropanes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149305323","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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Additive-Dependent Carboxylate-Carbonate Coordination Modulates Cu-C Homolysis and Radical Termination in Copper-Catalyzed Spirocyclization and Alkene Transposition: A DFT Study 添加剂依赖的羧酸-碳酸盐配位调节铜催化螺旋环化和烯烃转位中Cu-C均解和自由基终止：一项DFT研究

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-03 DOI: 10.1039/d6qo01387b

Yi Tang,Cui Lai,Abing Duan

{"title":"Additive-Dependent Carboxylate-Carbonate Coordination Modulates Cu-C Homolysis and Radical Termination in Copper-Catalyzed Spirocyclization and Alkene Transposition: A DFT Study","authors":"Yi Tang,Cui Lai,Abing Duan","doi":"10.1039/d6qo01387b","DOIUrl":"https://doi.org/10.1039/d6qo01387b","url":null,"abstract":"Copper-catalyzed cyclization and alkene-transposition cascades provide direct access to structurally complex spirocyclic ethers; however, the reaction medium contains multiple carboxylic acids, carbonate salts, and oxidants that can profoundly alter the copper coordination environment. Herein, density functional theory (DFT) calculations were employed to systematically investigate catalyst activation, oxycupration, Cu-C bond homolysis, transannular 1,5-hydrogen atom transfer (1, 5-HAT), radical capture, and β-H oxidative elimination. Unassisted Cu-C homolysis from the σ-alkyl Cu(II) intermediate is found to be strongly endergonic. In contrast, selected ion-paired environments containing acetate, pivalate, or bicarbonate provide accessible Cu-C homolysis pathways once the corresponding adducts are formed, whereas carbonate coordination, although thermodynamically favorable, stabilizes less reactive copper states. The four-membered-ring substrate exhibits a substantially higher 1, 5-HAT barrier than the larger-ring analogues, qualitatively consistent with its low experimental reactivity. Furthermore, acetate, pivalate, and bicarbonate support low-barrier β-H oxidative termination, while the carbonate-assisted pathway is markedly less favorable. These results establish an additive-dependent speciation framework: Cs2CO3 promotes deprotonation and neutralization of acetic acid but can concurrently give rise to carbonatebound resting states, whereas pivalate derived from PivOH favors coordination environments that are competent for both radical generation and termination. This framework identifies base identity, acid-base ratio, and ligand flexibility as experimentally testable parameters for tuning the accessible copper coordination environment and catalytic performance.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149305318","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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Metal-Free Access to Ketene Aminals and α-Phosphoryl Scaffolds via In Situ Thianthrenium Activation of N-Vinyl Azoles and Enamides n -乙烯基偶氮和烯酰胺的原位硫鎓活化对烯酮类动物和α-磷基支架的无金属获取

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-03 DOI: 10.1039/d6qo01273f

Susanta Patra,Satyajit Samanta,Shreyasi Jana,Parthasarathi Das

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Construction of SCF 3 -Containing Tetrahydropyridazines and Dihydropyrazoles via Photoredoxcatalytic Trifluoromethylthiolation/Cyclization of Unsaturated Aldehyde Hydrazones 不饱和醛腙光氧化催化三氟甲基硫基化/环化制备含四氢吡嗪和二氢吡唑的scf3

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-03 DOI: 10.1039/d6qo01304j

Congjun Zhu,Zilong Wang,Rui Yuan,Wenbo Yang,Kangning Cao,Tao Guo

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Beyond Phosgene: Recent Advances in the Catalytic Synthesis of Unsymmetrical Ureas 超越光气：催化合成不对称脲的最新进展

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-02 DOI: 10.1039/d6qo01440b

Shuhui Sun,Xiaowen Qin,Xiao-Feng Wu,Zhiping Yin

{"title":"Beyond Phosgene: Recent Advances in the Catalytic Synthesis of Unsymmetrical Ureas","authors":"Shuhui Sun,Xiaowen Qin,Xiao-Feng Wu,Zhiping Yin","doi":"10.1039/d6qo01440b","DOIUrl":"https://doi.org/10.1039/d6qo01440b","url":null,"abstract":"Unsymmetrical ureas are privileged scaffolds in pharmaceuticals and agrochemicals, yet their synthesis traditionally relies on toxic carbonylating agents. Recent years have witnessed a paradigm shift toward milder and more selective catalytic platforms, encompassing transition-metal catalysis, metal-free organocatalysis, photocatalysis, and electrochemistry. Noble metals (Pd, Rh, Ru, Ir) enable stereocontrolled access to chiral urea derivatives, whereas earth-abundant alternatives (Cu, Fe, Zn, Mn) expand synthetic accessibility with reduced cost. Metal-free systems offer particular advantages for peptide modification and late-stage pharmaceutical functionalization by circumventing metal-residue concerns, while photochemical and electrochemical methods harness renewable energy to drive radical-mediated urea bond formation under mild conditions. Tandem and cascade designs further facilitate the assembly of complex targets, including drug intermediates and radiolabeled probes. This review systematically compares these catalytic platforms in terms of mechanism, substrate scope, and practical utility, and concludes with a forward-looking perspective on sustainable and scalable urea synthesis.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"498 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149304791","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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An -insertion-driven water–lithium co-mediated 1,4-copper migration mechanism: enabling substituent-directed chemoselectivity in Cu-catalyzed alkyne functionalization 插入驱动的水-锂共介导的1,4-铜迁移机制：在cu催化的炔功能化中实现取代基定向化学选择性

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-02 DOI: 10.1039/d6qo01359g

Yuxia Liu,Xinhui Cao,Dongyu Zhu,Fei Li,Baoping Ling,Guang Chen,Pu Chen

{"title":"An -insertion-driven water–lithium co-mediated 1,4-copper migration mechanism: enabling substituent-directed chemoselectivity in Cu-catalyzed alkyne functionalization","authors":"Yuxia Liu,Xinhui Cao,Dongyu Zhu,Fei Li,Baoping Ling,Guang Chen,Pu Chen","doi":"10.1039/d6qo01359g","DOIUrl":"https://doi.org/10.1039/d6qo01359g","url":null,"abstract":"Cu-catalyzed C–H bond functionalization via 1,4-Cu migration represents an unconventional yet powerful synthetic strategy for accessing structurally diverse organosilanes. Herein, DFT calculations delineate the detailed mechanism of alkenylsilylmethylboronate formation from Cu-catalyzed coupling of tert-butyl(phenyl)acetylene with silylboronate (LiOtBu as an additive), with a particular focus on two unprecedented mechanistic innovations: (i) water–lithium co-mediated outer-sphere 1,4-Cu migration: in stark contrast to the canonical inner-sphere pathway prevalent in noble metal catalysis, our computational results reveal a kinetically preferred “water–lithium co-mediated outer-sphere” 1,4-Cu migration, explicitly incorporating previously overlooked water and lithium effects. (ii) Lithium-triggered anti-insertion initiation: this outer-sphere mechanism is initiated by anti-insertion of the alkyne substrate, rather than the commonly accepted syn-insertion paradigm. This distinct diastereoselectivity arises from an additional stabilizing interaction between (THF)Li and the adjacent alkyne carbon atom in the anti-insertion transition state. In addition, substituent variation (tBu → iPr) induces pronounced selectivity shifts, favoring the dominant formation of a tetrasubstituted alkene. Systematic evaluation predicts that the chemoselectivity from alkenylsilylmethylboronate to tetrasubstituted alkene products follows the order: tBu < iPr < Et < Me < H, with steric bulk directly correlating with selectivity magnitude. These results provide a foundational framework for rational catalyst design and selectivity control, advancing sustainable synthetic methodologies.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"63 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149304793","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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Oxidative vinylation annulation of ethyl tertiary amines for the construction of 4-arylpyrimido[1,2-a]benzimidazoles 乙基叔胺氧化乙烯基环化制备4-芳基嘧啶[1,2-a]苯并咪唑

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2026-11-02 DOI: 10.1039/d6qo01326k

Yingying Mei,Wanxin Su,Yubo Wang,Mengjie Li,Xu Zuo,Ziyun Bu,Qinghe Gao

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