Organic & Biomolecular Chemistry最新文献_第5页

Electronic and steric control of meso-tetraaryl porphycene tautomerism via regioselective β-functionalization. 通过区域选择性β功能化控制中四芳基卟啉互变异构的电子和空间控制。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob00853d

Debasish Mandal, Bhuban Mohan Bebarta, Mangalampalli Ravikanth

{"title":"Electronic and steric control of meso-tetraaryl porphycene tautomerism via regioselective β-functionalization.","authors":"Debasish Mandal, Bhuban Mohan Bebarta, Mangalampalli Ravikanth","doi":"10.1039/d6ob00853d","DOIUrl":"https://doi.org/10.1039/d6ob00853d","url":null,"abstract":"Herein, we establish the first synthetic strategy for the direct β-C-H nitration of a free base meso-tetraaryl porphycene using HNO3 in CHCl3 in a selective and controlled manner. The reaction affords two regioisomers of the β-nitro porphycene (regioselectivity upto β : β' = 3 : 7) without the formation of any over-nitrated products or compromising the integrity of the macrocycle. Beyond synthetic access, β-functionalization enables precise electronic and steric modulation of the porphycene macrocycle, resulting in distinct optical properties, including enhanced Q-band absorption and red-shifted near-infrared (NIR) fluorescence extending up to 720 nm with good quantum yields. Moreover, comprehensive spectroscopy, X-ray crystallography, and computational studies revealed that the β-selective nitration shows a strong electronic bias on the intrinsically rapid N-H tautomerization, establishing a highly biased equilibrium that majorly favours a single tautomeric state at room temperature within the rectangular cavity of the porphycene. Furthermore, the reduction of the electron-deficient β-nitro porphycene to an electron-rich β-amino porphycene reverses the electronic perturbation and favours the opposite tautomeric form. This simple protocol provides electronically tuned β-functionalized porphycenes that not only serve as promising building blocks to design molecular systems for finely tuned NIR emissive optoelectronics, biological and material applications, but also act as model substrates to study the fundamentally important hydrogen transfer in porphycene macrocycles.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177911","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Ruthenium-catalyzed asymmetric transfer hydrogenation of [2.2]paracyclophanecarboxaldehydes via kinetic resolution. 钌催化的[2.2]副环蒽醛的不对称转移加氢动力学分解。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01308b

Yu Yang, Jia-Xuan Wang, Hao-Dong Chen, Chang Chen, Yong-Gui Zhou, Bo Wu, Chang-Bin Yu

引用次数: 0

Electrochemical C4-C4' homocoupling of 2-arylpyridines. 2-芳基吡啶的电化学C4-C4′均偶联。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01238h

Jialing Zhang, Zishen Song, Li Wang, Laizheng Luo, Yuxiang Gao, Jinwei Zhang, Weisi Guo

引用次数: 0

Synthesis of β,N-diphosphoryl-substituted α-aminocinnamates via the C,N-diphosphorylation of 2H-azirines. 2h -氮嘧啶C， n -二磷酸化合成β， n -二磷酸基取代α-氨基氨基酸酯。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01327a

Ilya A Romanenko, Anastasiya V Agafonova, Ilya A Smetanin, Maksim A Valiarovskii, Alexander F Khlebnikov, Mikhail S Novikov

引用次数: 0

Ternary deep eutectic solvent-mediated direct amidation of carboxylic acids. 三元深共晶溶剂介导的羧酸直接酰胺化。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01305h

Yumiao Zhao, Yujia Jiang, Xiaoqiang Yu

引用次数: 0

Studies on the convenient synthesis, fluorescence properties and bioactivity of chromenonitriles. 铬腈的便捷合成、荧光性质及生物活性研究。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01096b

Sheng-Yu Li, Zhong-Hao Li, Chu-Ming Pang, Ye-Tong Liu, Bo-Wen Wang, Zu-Qi Zhang, Ying-Jun Zhang, Zhao-Yang Wang

{"title":"Studies on the convenient synthesis, fluorescence properties and bioactivity of chromenonitriles.","authors":"Sheng-Yu Li, Zhong-Hao Li, Chu-Ming Pang, Ye-Tong Liu, Bo-Wen Wang, Zu-Qi Zhang, Ying-Jun Zhang, Zhao-Yang Wang","doi":"10.1039/d6ob01096b","DOIUrl":"https://doi.org/10.1039/d6ob01096b","url":null,"abstract":"The synthesis of chromenonitriles remains largely underexplored, primarily due to the limited availability of suitable substrates and the generally unsatisfactory yields of existing methods. Herein, we report a new method that enables the efficient construction of chromenonitriles under mild, metal-free conditions, using readily accessible chromones and benzoylacetonitriles as starting materials. This transformation is driven by a Knoevenagel condensation co-catalyzed by pyridine and 1,4-diazabicyclo[2.2.2]octane (DABCO), affording the desired products in good yields. In addition to the reported compounds 3a, 3d and 3h, 23 other new compounds are also successfully synthesized. Photophysical characterization reveals that the synthesized compounds exhibit intense yellow-green fluorescence and pronounced aggregation-induced emission (AIE) behaviour, observable both in a dilute solution and the solid state. Dynamic light scattering analysis confirms the correlation between aggregation and fluorescence enhancement, and DFT calculations rationalize the observed photophysical behaviour. Antibacterial activity tests show that they have the potential to become fluorescent probes with antibacterial ability.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":"24 39","pages":"8093-8100"},"PeriodicalIF":2.8,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

A practical guide to atropisomerism: fundamentals and case studies from modern drug discovery. 萎缩异构的实用指南：现代药物发现的基础和案例研究。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01244b

Mariami Basilaia, Andrew M O'Brien, Michael R Rufrano, Jeffrey L Gustafson

{"title":"A practical guide to atropisomerism: fundamentals and case studies from modern drug discovery.","authors":"Mariami Basilaia, Andrew M O'Brien, Michael R Rufrano, Jeffrey L Gustafson","doi":"10.1039/d6ob01244b","DOIUrl":"https://doi.org/10.1039/d6ob01244b","url":null,"abstract":"Atropisomerism is a form of axial chirality that arises when rotation about a single bond is sufficiently restricted to render the enantiomeric conformers configurationally stable and isolable. Because bond rotation provides a spontaneous pathway for racemization, atropisomers span an extraordinary range of stereochemical stabilities-from species that racemize within seconds at room temperature to compounds predicted to retain their configuration for milenia under any pharmaceutically relevant conditions. Although atropisomerism is most commonly associated with biaryl scaffolds, it can arise across a remarkably diverse range of molecular architectures. Many of these have emerged as privileged pharmaceutical scaffolds, making atropisomerism an increasingly important consideration in medicinal chemistry, with more than 20 configurationally stable atropisomeric drug candidates currently in clinical development worldwide. Consequently, atropisomerism has evolved from a topic of primarily academic interest into a common and practical challenge in modern drug discovery and development. In this review, we discuss the challenges associated with the discovery, development, and manufacturing of atropisomeric drug candidates, culminating in a survey of the strategies used to establish atropisomeric axes on process scale for approved drugs and compounds currently undergoing clinical evaluation. We hope this review will serve as both a practical resource and a source of inspiration for chemists developing the next generation of atropisomerically pure pharmaceuticals.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Solvent-controlled divergent (4 + 1) cycloaddition of 1,4-enynoates with amines: modular synthesis of pyrroles. 溶剂控制的1,4-乙烯酸酯与胺的发散（4 + 1）环加成：吡咯的模块化合成。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01271j

Jianghong Tan, Lu Zhang, Dale Wu, Haibin Yu, Zhongyan Cao, Bin Yu, Er-Qing Li

引用次数: 0

Pd-catalyzed allene hydroarylation with ArI/TsNHNH₂: access to new fluorinated α-amino acid derivatives. 用ArI/TsNHNH2催化丙烯氢化芳基化：获得新的氟化α-氨基酸衍生物。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-14 DOI: 10.1039/d6ob01242f

Alexandra S Bubnova, Alexander A Martyanov, Pavel S Gribanov, Anna N Philippova, Daria V Vorobyeva, Alexander F Smol'yakov, Ivan A Godovikov, Sergey N Osipov

引用次数: 0

Heterologous expression of the Metarhizium anisopliae barc gene cluster reveals a diphenyl ether-to-xanthene transformation in barceloneic acid biosynthesis. 绿僵菌barc基因簇的异源表达揭示了巴塞罗纳酸生物合成中二苯基醚向杂蒽的转化。

IF 2.8 3区化学

Organic & Biomolecular Chemistry Pub Date : 2026-10-13 DOI: 10.1039/d6ob01032f

Nicolau Sbaraini, Joe Bracegirdle, Chin-Soon Phan, Brodie W Bulcock, Felipe Geremia, Matheus da Silva Camargo, Gavin R Flematti, Ernest Lacey, Charley C Staats, Andrew M Piggott, Yit-Heng Chooi

{"title":"Heterologous expression of the Metarhizium anisopliae barc gene cluster reveals a diphenyl ether-to-xanthene transformation in barceloneic acid biosynthesis.","authors":"Nicolau Sbaraini, Joe Bracegirdle, Chin-Soon Phan, Brodie W Bulcock, Felipe Geremia, Matheus da Silva Camargo, Gavin R Flematti, Ernest Lacey, Charley C Staats, Andrew M Piggott, Yit-Heng Chooi","doi":"10.1039/d6ob01032f","DOIUrl":"https://doi.org/10.1039/d6ob01032f","url":null,"abstract":"Filamentous fungi generate chemical diversity through several evolutionary strategies, including the elaboration of conserved biosynthetic intermediates into structurally distinct secondary metabolites. Emodin and its corresponding anthrone are central intermediates in fungal aromatic polyketide metabolism, yet the enzymatic logic that remodels these precursors into more complex scaffolds remains incompletely understood. To investigate this process, we examined an infection-responsive non-reducing polyketide synthase biosynthetic gene cluster (barc) from the entomopathogenic fungus Metarhizium anisopliae predicted to encode an emodin-derived aromatic polyketide pathway. Heterologous reconstruction of the barc cluster in Aspergillus nidulans led to the production of the previously reported diphenyl ether barceloneic acid A (1) and the xanthene barceloneic acid C2 (2), together with two new compounds derived from 2, barceloneic acids D and E (3 and 4). Compound 3 is a cyclopentanone adduct of the xanthene 2, whereas 4 is a polyketide-indole hybrid, highlighting the chemical reactivity of the xanthene 2 scaffold. Through combinatorial heterologous expression and feeding assays, we identified a predicted glucose-methanol-choline oxidoreductase (BarcL) as the enzyme responsible for converting diphenyl ether 1 to xanthene 2. This defines a previously uncharacterised oxidative scaffold-remodelling step in barceloneic acid biosynthesis, revealing how an emodin-derived pathway can access a xanthene scaffold. Deletion of the backbone gene barcB in M. anisopliae did not significantly alter virulence towards Tenebrio molitor (mealworm) under the conditions tested, suggesting that barceloneic acids are not essential for pathogenicity in this insect model.","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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