Journal of Organic Chemistry最新文献

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Solvent-Free α-Arylation Reaction of Ketones with (Hetero)aryl Chlorides by N-Heterocyclic Carbene–Palladium Complex (SIPr)Ph2Pd(cin)Cl n -杂环碳钯配合物（SIPr）Ph2Pd(cin)Cl与（杂）芳基氯化物的无溶剂α-芳基化反应

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-09 DOI: 10.1021/acs.joc.5c02510

Jia-Sheng Ouyang,Xiaoling Wang,Huizhen Jiang,Ruiyong Luo,Liqun Hu,Yaqi Zhang,Liqin Qiu

A green and mild palladium-catalyzed solvent-free α-arylation reaction of ketones was disclosed for the first time. Using the robust N-heterocyclic carbene–palladium complex (SIPr)Ph2Pd(cin)Cl, (hetero)aryl chlorides and ketones were able to generate monoarylation products in excellent yields under solvent-free conditions, with a total of 41 examples. Furthermore, the protocol has been demonstrated to be suitable for multigram-scale preparation with a high yield.

引用次数: 0

Harperoids A–F, Complex Polyprenylated Acylphloroglucinols from Harrisonia perforata that Reverse Multidrug Resistance by Targeting ABC Transporter Function 通过靶向ABC转运蛋白功能逆转多药耐药的孔花果中的复合聚戊烯化酰基间苯三酚A-F

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-09 DOI: 10.1021/acs.joc.5c03053

Pei-Pei An,Ying Li,Jin-Hai Yu,Bin Zhou,Jian-Min Yue

Utilizing an LC/MS-MS-based feature-based molecular networking (FBMN) strategy, six undescribed PPAPs (1–6) characterized by an acetyl substituent at the C-1 position of their phloroglucinol scaffold, were efficiently isolated from the roots of Harrisonia perforata. Notably, compund 1 displays an unconventional 5/5/6/5 ring architecture, while compounds 5 and 6 represent the first case incorporating a benzofuran core and a geranyl-derived cyclohexanol unit. Their structures were unequivocally elucidated through comprehensive spectroscopic data analysis, TDDFT-ECD calculations, and X-ray crystallographic studies. Interestingly, compound 3 at 20 μM exhibited negligible cytotoxicity but significantly potentiated the activity of paclitaxel against HCT-15 cells by 42.8-fold. Mechanistic studies further demonstrated that compound 3 did not significantly alter the expression levels of ATP-binding cassette (ABC) transporters, but potently inhibited the transport function of both ABCB1 and ABCG2. Molecular docking reveals that compound 3 stably binds to the central substrate-binding cavities of ABCB1 and ABCG2, with its binding primarily stabilized by hydrogen bonds and hydrophobic interactions.

{"title":"Harperoids A–F, Complex Polyprenylated Acylphloroglucinols from Harrisonia perforata that Reverse Multidrug Resistance by Targeting ABC Transporter Function","authors":"Pei-Pei An,Ying Li,Jin-Hai Yu,Bin Zhou,Jian-Min Yue","doi":"10.1021/acs.joc.5c03053","DOIUrl":"https://doi.org/10.1021/acs.joc.5c03053","url":null,"abstract":"Utilizing an LC/MS-MS-based feature-based molecular networking (FBMN) strategy, six undescribed PPAPs (1–6) characterized by an acetyl substituent at the C-1 position of their phloroglucinol scaffold, were efficiently isolated from the roots of Harrisonia perforata. Notably, compund 1 displays an unconventional 5/5/6/5 ring architecture, while compounds 5 and 6 represent the first case incorporating a benzofuran core and a geranyl-derived cyclohexanol unit. Their structures were unequivocally elucidated through comprehensive spectroscopic data analysis, TDDFT-ECD calculations, and X-ray crystallographic studies. Interestingly, compound 3 at 20 μM exhibited negligible cytotoxicity but significantly potentiated the activity of paclitaxel against HCT-15 cells by 42.8-fold. Mechanistic studies further demonstrated that compound 3 did not significantly alter the expression levels of ATP-binding cassette (ABC) transporters, but potently inhibited the transport function of both ABCB1 and ABCG2. Molecular docking reveals that compound 3 stably binds to the central substrate-binding cavities of ABCB1 and ABCG2, with its binding primarily stabilized by hydrogen bonds and hydrophobic interactions.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Cr(III)-Salen-Catalyzed Enantioselective C3-Aryloxylation of Spiroepoxy Oxindoles Cr(III)- salen催化螺环氧氧吲哚的对映选择性c3 -芳基化反应

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-09 DOI: 10.1021/acs.joc.5c02576

Ananda Shankar Mondal,Arindam Jana,Ayan Chatterjee,Kumaresh Ghosh,Saumen Hajra

We report the first metal-salen-catalyzed switchable ortho-C- and O-alkylation of phenols with spiroepoxides at the tertiary sp3-carbon center of spiroepoxides. Catalyst choice between chiral Cr(III)-salen and chiral Co(III)-salen OTf enables a rare divergence in reactivity: the chiral salen Cr(III)Cl catalyst directs the reaction toward highly enantioselective C3-aryloxylation to afford 3-aryloxy-oxindole-3-methanols (up to 98% ee), whereas salenCo(III)OTf (cat. B) switches the outcome to the complementary C3-ortho-arylation pathway without stereoinduction. The method tolerates various N-protecting groups and aromatic substitution patterns, creating a diverse library of functionalized oxindoles. Mass spectrometric studies reveal catalyst–substrate complexes and (hetero)dimeric assemblies, providing insight into a mechanistic pathway that favors aryloxylation. The method also achieves the first asymmetric synthesis of spiro[benzo[b][1,4]dioxine-2,3′-indolin]-2′-one.

引用次数: 0

Six-Component Telescope Assembly of sp3-Rich Hexahydro-pyrrolo[3,4-c]pyridine-1,6-diones via Sequential Enaminone Formation, Aza-Annulation, Hydrogenation, and Ugi Cyclization 富sp3六氢吡咯[3,4-c]吡啶-1,6-二酮的序序胺酮生成、偶氮环化、氢化和Ugi环化六组分望远镜组装

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-08 DOI: 10.1021/acs.joc.5c02621

Ainara Bekbolatova,Azat M. Makhmet,Azamat Begenov,Sofia D. Martynova,Niyaz Amire,Anton A. Nechaev,Rakhmetulla Yerkassov,Andrey Belyaev,Davit Hayrapetyan,Anatoly A. Peshkov,Vsevolod A. Peshkov

We report a six-component, four-step telescope sequence that enables rapid access to structurally complex, sp3-enriched hexahydro-1H-pyrrolo[3,4-c]pyridine-1,6(2H)-dione scaffold. The streamlined protocol integrates enaminone formation, intramolecular aza-annulation, heterogeneous alkene hydrogenation, and a three-component Ugi cyclization within a single operational sequence requiring only one purification step. This approach unites multicomponent and tandem reaction principles to deliver diastereomerically defined products featuring four contiguous stereocenters. The method demonstrates high atom economy and modular diversification through systematic variation of isocyanide and amine inputs.

引用次数: 0

Synthesis of 3,5-Disubstituted-(1H-) and (2H-) Heteroaryl-1,2,4-triazoles via an Oxidative Annulation Strategy. 氧化环化合成3,5-二取代-(1H-)和（2H-）杂芳基-1,2,4-三唑。

IF 3.6 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-07 DOI: 10.1021/acs.joc.5c03029

Emmanuel E Aimiuwu, Damian P Duda, Allen G Oliver, David A Dixon, Jesse D Carrick

1,2,4-Triazole is a ubiquitous heterocycle of significance for pharmaceuticals, materials, and ligand design. A convergent, atom-economical strategy for the construction of this important moiety has been developed, leveraging functionalized heteroaryl hydrazonimides and carbaldehydes via iodine-mediated oxidative annulation in an efficient, scalable, and metal-free manner, providing completely chemoselective 1H- or 2H-3,5-disubstituted-1,2,4-triazoles of relevance to separation science and medicinal chemistry. The twenty-nine-example substrate scope is highlighted by rapid access to sp²- and sp³-hybridized substituents through carbaldehyde selection. Diversely functionalized pyridyl- and heteroaryl components were incorporated through a hydrazonimide synthon with several examples having relevance to unsymmetric, soft-N-donor complexant scaffolds utilized in minor actinide extraction in support of improving the sustainability of the nuclear fuel cycle. Single-crystal X-ray diffraction experiments confirmed the presence of 1H- and 2H-tautomers. Density functional theory computations provided support of a proposed mechanistic hypothesis. Method optimization, substrate scope, scale-up experiments, and a preliminary reaction mechanism are reported herein.

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引用次数: 0

Silver-Catalyzed Enantioselective and Diastereoselective Aldol Reaction of α-Isocyanoacetates with Aldehydes Enabled by Cinchona-Derived Amide Adamantylphosphine Ligands. 银催化α-异氰酸酯与氨基金刚烷膦配体醛的对映选择性和非对映选择性醛醇反应。

IF 3.6 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-07 DOI: 10.1021/acs.joc.5c02366

Yulong Jiang, Xianghua Zhao, Xinyu Chen, Zhengguo Deng, Dingguo Song, Fei Ling, Weihui Zhong

By modifying Dixon's ligands, cinchona-derived amide adamantylphosphine ligands were synthesized. When combined with silver salts, these ligands enabled highly efficient asymmetric aldol reactions using isocyanoacetates as eco-friendly C-N synthons. The catalytic system operated under mild conditions with accelerated kinetics, affording chiral oxazolines in up to 99% ee and >99:1 dr. Broad substrate scope was demonstrated with both aryl and alkyl aldehydes, and the method enabled atom-economical synthesis of key intermediates for thiamphenicol and chloramphenicol.

引用次数: 0

Divergent Access to Optically Active Butenolides via Tandem C–H Activation and Michael Addition Enabled by Rh/Cinchonine Catalysis 通过串联C-H活化和Rh/Cinchonine催化的Michael加成获得不同的光学活性丁烯内酯

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-06 DOI: 10.1021/acs.joc.5c02777

Dattatraya H. Dethe, Arsheed Ahmad Bhat

We report a highly enantioselective and efficient synthesis of C-3 substituted butenolides via a tandem C–H activation/Michael addition cascade, enabled by Rh/cinchonine dual catalysis. This strategy leverages the stability and accessibility of the achiral [Cp*RhCl₂]₂ complex in combination with the chiral induction provided by the naturally occurring alkaloid cinchonine, eliminating the need for complex chiral ligands. Importantly, this dual catalytic system represents the first enantioselective protocol that exploits simple acrylic acids as coupling partners, thereby extending the reactivity paradigm beyond conventional benzoic acid derivatives and significantly broadening the substrate scope beyond aromatic counterparts. The reaction proceeds in a one-pot fashion under mild conditions, delivering a wide range of products with good to very good enantiomeric excess.

引用次数: 0

Microwave-Assisted One-Pot Synthetic Pathways for Pyrido[2,3-d]imidazole Derivatives 微波辅助一锅合成吡哆[2,3-d]咪唑衍生物的途径

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-06 DOI: 10.1021/acs.joc.5c01864

Bartosz Orwat, Sylwia Raczak, Kamila Jankowska, Grzegorz Krajewski, Julita Nawrocik, Maciej Kubicki, Rafał Januszewski, Beata Łuszczyńska, Ireneusz Kownacki

Herein, we report efficient microwave-assisted one-pot protocols, enabling the efficient synthesis of a broad scope of functionalized pyrido[2,3-d]imidazoles. The developed methodologies allow obtaining target compounds using cheap reagents and catalysts, in very short reaction times, and perform three-step reactions in the same vessel without the need of intermediate isolation. The obtained pyridoimidazoles equipped with alkyl, alkoxy, hydroxy, halogen, acyl, and amino substituents were fully characterized and constitute useful materials for coordination chemistry or building blocks for further transformations.

引用次数: 0

Cobalt-Catalyzed Asymmetric Reductive Propargylic Addition of α-Ketimino Esters 钴催化α-酮胺酸酯的不对称丙炔还原加成

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-06 DOI: 10.1021/acs.joc.5c02793

Ning Liu, Zhiying Yu, Wenyu Zhao, Xianqing Wu, Jingping Qu, Yifeng Chen, Wei-Hong Zhu

The Nozaki–Hiyama–Kishi (NHK) reaction serves as a powerful method for stereoselective carbon–carbon bond formation under mild conditions. While significant progress has been made in the enantioselective propargylation of carbonyl compounds, its application to imines remains underdeveloped. Herein, we report a catalytic asymmetric reductive propargylic addition to α-ketimino esters, providing direct access to chiral propargylated amines with high chemoselectivity and enantioselectivity. This method expands the synthetic utility of NHK-type reactions toward nitrogen-containing scaffolds, offering a complementary route to enantioenriched amine derivatives under mild and efficient conditions.

引用次数: 0

Unveiling the Electronic Effects of the Lewis Acids in Nucleophilic Substitution Reactions from a Molecular Electron Density Theory Perspective 从分子电子密度理论的角度揭示路易斯酸在亲核取代反应中的电子效应

IF 4.354 2区化学 Q1 CHEMISTRY, ORGANIC

Journal of Organic Chemistry

Pub Date : 2026-02-06 DOI: 10.1021/acs.joc.5c02214

Luis R. Domingo, Maria José Aurell, Patricia Pérez

The electronic effects of Lewis acids (LAs) in nucleophilic substitution (SN) reactions are investigated from a molecular electron density theory (MEDT) perspective at the ωB97X-D/6-311G(d,p) level in dichloromethane. The LA-catalyzed ring-opening of two sulfonyl aziridines, typically classified as S_N2-type processes, is analyzed, and the LA-assisted SN reactions of three N-alkylmethanesulfonamides toward the chloride anion. LAs do not significantly increase the electrophilicity ω of the substrate but markedly enhance the nucleofugality Λ of the sulfonamide-leaving group (LG), which governs SN feasibility. LAs lower activation enthalpies by over 17 kcal·mol^–1, rendering the ring-opening of 2-phenylaziridines fully regioselective. Electron-density topological analyses show that at the transition-state structures (TSs), the C–N bond associated with the LG is already broken, whereas C–Cl bond formation has not begun, indicating a carbocation-like structure at the central carbon. A relative interacting atomic energy analysis of the LA-catalyzed ring-opening of 1-methanesulfonylaziridine by the chloride anion in the presence of Me₄N⁺ reveals that stabilization of both the sulfonamide:LA LG and chloride accounts for the reduced activation barriers. LAs such as BF₃ and AlCl₃ enhance the LG ability (nucleofugality Λ) of sulfonamides, shifting the TS toward a more carbocation-like (S_N1-like) structure and lowering the nucleophile participation.

{"title":"Unveiling the Electronic Effects of the Lewis Acids in Nucleophilic Substitution Reactions from a Molecular Electron Density Theory Perspective","authors":"Luis R. Domingo, Maria José Aurell, Patricia Pérez","doi":"10.1021/acs.joc.5c02214","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02214","url":null,"abstract":"The electronic effects of Lewis acids (LAs) in nucleophilic substitution (SN) reactions are investigated from a molecular electron density theory (MEDT) perspective at the ωB97X-D/6-311G(d,p) level in dichloromethane. The LA-catalyzed ring-opening of two sulfonyl aziridines, typically classified as SN2-type processes, is analyzed, and the LA-assisted SN reactions of three N-alkylmethanesulfonamides toward the chloride anion. LAs do not significantly increase the electrophilicity ω of the substrate but markedly enhance the nucleofugality Λ of the sulfonamide-leaving group (LG), which governs SN feasibility. LAs lower activation enthalpies by over 17 kcal·mol–1, rendering the ring-opening of 2-phenylaziridines fully regioselective. Electron-density topological analyses show that at the transition-state structures (TSs), the C–N bond associated with the LG is already broken, whereas C–Cl bond formation has not begun, indicating a carbocation-like structure at the central carbon. A relative interacting atomic energy analysis of the LA-catalyzed ring-opening of 1-methanesulfonylaziridine by the chloride anion in the presence of Me4N+ reveals that stabilization of both the sulfonamide:LA LG and chloride accounts for the reduced activation barriers. LAs such as BF3 and AlCl3 enhance the LG ability (nucleofugality Λ) of sulfonamides, shifting the TS toward a more carbocation-like (SN1-like) structure and lowering the nucleophile participation.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"302 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

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