Organic Chemistry Frontiers最新文献

{"title":"Copper catalyzed aerobic oxidation of aldehydes to carboxylic acids","authors":"Yankai Huang, Sheng Jiang, Zhengnan Zhengnan Zhou, Yibo Yu, Hui Qian, Shengming Ma","doi":"10.1039/d5qo00330j","DOIUrl":"https://doi.org/10.1039/d5qo00330j","url":null,"abstract":"An efficient practical aerobic oxidation of aldehydes to carboxylic acids using O2 or air as the oxidant has been developed. The reaction was carried out with a catalytic amount each of Cu(NO3)2·3H2O and TEMPO at room temperature tolerating many useful functional groups such as alkynyl, amino, aryl, etc. Complex molecules and compounds containing multiple aldehyde groups are applicable to this reaction with an excellent selectivity. Gram scale reactions have been easily conducted.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"14 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876084","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}

{"title":"A Cascade Markovnikov Addition / Lewis Acid-Catalyzed Rearrangement of Methyleneaziridines and Carboxylic Acids: Continuous-Flow Synthesis of α-Amidoketones","authors":"Bin Pan, Haotian Sun, Feng Li, Qing-Bao Zhang, Shanshan Zhang, Jia-Hao Wang, Meng-Rui Xu, Jing-Tian Ge, Zi-Qing Hu, Shang Lv, Lijuan Feng, Guofu Huang","doi":"10.1039/d5qo00495k","DOIUrl":"https://doi.org/10.1039/d5qo00495k","url":null,"abstract":"α-Amidoketones are essential structural motifs in pharmaceuticals and synthetic chemistry. In this study, we describe a novel synthetic method that involves a cascade addition reaction, followed by a Lewis acid-catalyzed rearrangement of methyleneaziridines and carboxylic acids. Additionally, we developed a high-speed continuous flow synthesis method, allowing the reaction to proceed efficiently within 3.5 minutes. The incorporation of a greener silica gel-packed catalyzed column in this continuous flow system effectively facilitates the rearrangement step, providing a more environmentally friendly approach for synthesizing α-amidoketone compounds.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"71 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872746","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}

{"title":"Mechanistic Insights into Ni–Al Co-Catalyzed Alkyne Carbophosphination Enabled by C–P Bond Activation","authors":"Congcong Huang, Yishi Li, Juan Li","doi":"10.1039/d5qo00453e","DOIUrl":"https://doi.org/10.1039/d5qo00453e","url":null,"abstract":"Nickel–aluminum (Ni–Al) bimetallic catalysis has demonstrated remarkable efficiency in C–P bond activation, yet its underlying mechanism remains elusive. Key questions regarding the synergistic roles of Ni and Al, the advantages of the dual-catalyst system, and the effect of the substrate and ligand are critical for advancing this strategy. Here, we employ density functional theory (DFT) calculations to systematically investigate the Ni–Al cooperative catalysis mechanism, focusing on the interplay between Ni and Al, the impact of AlMe₂Cl, the role of PPh₃, and the effect of substituents on reaction efficiency. We explored two cooperative models for Ni–Al interactions and found that the uncommon Ni–LA interaction (Model A) is more favorable than the Ni–LA–L bridged system (Model B). This preference arises because the use of PPh₃ makes phenyl migration or phenyl dehydrogenation highly unfavorable, thereby directing the reaction toward Model A as the optimal pathway. Our results demonstrate that AlMe₂Cl plays a crucial role in stabilizing key transition states through non-covalent interactions, charge redistribution, electrostatic stabilization, and electron density distribution, as well as modulating HOMO and LUMO energies, effectively lowering activation barriers. Additionally, PPh₃ enhances reaction efficiency by facilitating stabilizing non-covalent interactions, strengthening Ni coordination through a Ni–P bond, and optimizing charge transfer. Furthermore, an analysis of substrate effects reveals that both steric congestion and electronic stabilization influence reaction efficiency, with smaller and more electronically favorable substituents facilitating charge transfer, lowering oxidative addition barriers, and leading to higher experimental yields. These findings provide a detailed mechanistic understanding of Ni–Al bimetallic catalysis in C–P bond activation and offer guiding principles for the rational design of more efficient catalytic systems. The study not only clarifies the synergistic roles of Ni and Al but also highlights the critical influence of ligands and substrate effects in optimizing reaction outcomes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872747","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}

{"title":"meta-Selective thiofluoroalkylation of substituted pyridines via Zincke imines","authors":"Will Connor Hartley, Arnau Huerta, Júlia C. Negredo, Omar Boutureira","doi":"10.1039/d5qo00533g","DOIUrl":"https://doi.org/10.1039/d5qo00533g","url":null,"abstract":"Zincke imines enable the regioselective thiofluoroalkylation of substituted pyridines, grating access to thioalkylated pyridines bearing a range of fluorination patterns. Crucial to success of this strategy was the use of saccharine-derived thiofluoroalkylating reagents, which, upon reaction with TMSCl, generate electrophilic sulfenyl chlorides.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876086","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}

{"title":"Conformational Preference of N-Difluoromethylated Amides: Contributions of Hydrogen-Bonding, Steric, and Stereoelectronic Effects","authors":"Ryu Yamasaki, Ami Tashiro, Chisaki Sato, Ai Ito, Iwao Okamoto","doi":"10.1039/d5qo00497g","DOIUrl":"https://doi.org/10.1039/d5qo00497g","url":null,"abstract":"Fluorine, possessing the highest electronegativity among all elements, is frequently introduced to modify the structure and properties of compounds. Among fluorine-containing substituents, the difluoromethyl group is regarded as a bioisostere of a hydroxyl or isopropyl group, but its effect on the conformation of amides has not been thoroughly investigated. This study presents a detailed analysis of the conformational preferences of <em>N</em>-difluoromethylated amides and the effects of the difluoromethyl group, focusing on hydrogen-bonding, steric and stereoelectronic effects. <em>N</em>-Difluoromethylated amides were synthesized directly from amides using TMSCF<small>₂</small>Br and tBuONa as a base. NMR analysis revealed that <em>N</em>-difluoromethylated anilides preferentially adopt cis conformation, whereas a phenylalanine derivative favors trans conformation. DFT calculations suggest that the difluoromethyl group interacts with both the carbonyl group and a phenyl group, but repulsion between the carbonyl oxygen and phenyl group and <em>n</em>(O) → π*<small>_C=O</small> interaction play major roles in determining the conformational preferences. In addition, the trans conformer of the <em>N</em>-difluoromethylated phenylalanine derivative is stabilized by electron donation from fluorine, enhancing amide resonance.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872745","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}

{"title":"Bis-Fischer Indole[3,2-b]carbazole Modification of [10]Cycloparaphenylenes: Tuning Optical Properties Through Rigid Substitution","authors":"Wanchun Duan, Dongming Chen, Dang Zhen, Shidong He, Wanqun Hu, Lu-Yuan Hao, Xin Xu","doi":"10.1039/d5qo00539f","DOIUrl":"https://doi.org/10.1039/d5qo00539f","url":null,"abstract":"The rigid bis-Fischer indolo[3,2-b]carbazole and [n]cycloparaphenylenes ([n]CPP) have garnered interest due to their unique electronic behavior and optoelectronic properties. We have combined 2,8-di-tert-butyl-5,11-dihydroindolo [3,2-b]carbazole (BH-ICZ) with [10]CPP to form BH-ICZ[10]CPP, where the introduced BH-ICZ fragment reduces the symmetry of the original [10]CPP parent structure, and amplifies the previously weak absorption band at 450 nm. Compared with unmodified [10]CPP, the fluorescence wavelength shows a significant redshift, and the solvatochromic effect becomes more pronounced with increasing solvent polarity, reaching 553 nm in dimethyl sulfoxide. Its photoluminescence quantum yield (PLQY) initially increases and then decreases, peaking at 0.92 in dichloromethane, which is significantly higher than that of both [10]CPP and BH-ICZ. Calculations highlight the origin of intramolecular charge transfer within BH-ICZ[10]CPP and the elimination of Laporte-forbidden transitions. The interaction between the BH-ICZ fragment and the solvent enhances the solvatochromic effect, underscoring the critical role of the introduced fragment in tuning fluorescence behavior. This research makes it a promising and worthwhile area for exploration.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872748","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}

{"title":"Acidic pH Modulated Photoswitching of Sulfur-bridged Seven-membered Cyclic Azopyridines","authors":"Fengying Lan, Cefei Zhang, Zhihao Liu, Sitong Li, Jinmeng Yan, Xiaohu Zhao, Changwei Hu, Zhishan Su, Pengchi Deng, Zhipeng Yu","doi":"10.1039/d5qo00315f","DOIUrl":"https://doi.org/10.1039/d5qo00315f","url":null,"abstract":"Azoarene molecular photoswitches with bistability are a family of widely employed structure-tuning units for photopharmacology and smart material construction. Notably, medium-ring azobenzenes, especially seven-membered dibenzo[<em>b</em>,<em>f</em>][1,4,5]thiadiazepines (DBTD), are characterized as fast-responsive T-type molecular photoswitches with particular features for light-energy conversion to ring-strain energy. The burgeon of azoheteroarenes with enhanced bistability and solubility have considerably broadened the horizon of their utilization. Herein, we present a novel class of seven-membered cyclic azoheteroarenes, benzo[<em>b</em>]pyrido[<em>f</em>][1,4,5]thiadiazepines (BPTD) and dipyrido[2,3-<em>b</em>:3',2'-<em>f</em>][1,4,5]thiadiazepine (DPTD). The integration of pyrido-heteroarenes in BPTD and DPTD enables pH-modulated T-type photoswitching performance spanning from pH = -0.33 to 7.0, distinguishing them from DBTD. Importantly, benzo[<em>b</em>]pyrido[3,4-<em>f</em>][1,4,5]thiadiazepine (3-BPTD) exhibits slightly enhanced photoswitching amplitude (photostationary distribution of <em>E</em>-isomers) as well as decent photo- and thermal stability in highly acidic environments. These features make them promising T-type photoswitches for potential acid-resistant light-energy converters and acid-endurable fast-responsive smart materials.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"260 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866483","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}

{"title":"Chiral phosphoric acid catalyzed asymmetric synthesis of C−N axially chiral uracils with antitumor activity through kinetic resolution strategy","authors":"Jiawei Xu, Haisong Xu, Yunyi Xu, Zhong-Qi Peng, Wei Zhang, Xin Li","doi":"10.1039/d5qo00144g","DOIUrl":"https://doi.org/10.1039/d5qo00144g","url":null,"abstract":"An efficient method for the asymmetric synthesis of C−N axially chiral uracils has been developed by kinetic resolution of 6-NH2-substituted uracils with achiral azlactones, using chiral phosphoric acid-catalyzed asymmetric acylation. A broad range of 6-NH2 uracils were resolved with high efficiency and enantioselectivity, achieving a selectivity factor of up to 276. DFT calculations revealed the origins of the enantioselectivity. Large-scale reaction and straightforward transformations of the chiral products highlighted the practical value of this methodology. Furthermore, potential antitumor agents were identified through cellular assays, illustrating the synthetic utility of this approach.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866793","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}

{"title":"Palladium-catalyzed double strain-release (3+3) cycloaddition for the synthesis of vinylbicyclo[3.1.1]heptanes","authors":"Xin-Yu Gao, Yuanjiu Xiao, Xuan Zhan, Yu-Jie Li, Kun-Ju Wang, Jian-Jun Feng","doi":"10.1039/d5qo00460h","DOIUrl":"https://doi.org/10.1039/d5qo00460h","url":null,"abstract":"All-carbon bicyclo[3.1.1]heptanes are important structural motifs in bioactive compounds and serve as bioisosteres for substituted benzenes. However, their synthesis, especially through polar (3+3) cycloaddition strategies, remains underexplored. Herein, we present a palladium-catalyzed double strain-release (3+3) cycloaddition involving bicyclo[1.1.]butanes (BCBs) and vinylcyclopropanes. The reaction tolerates a variety of BCBs and vinylcyclopropane derivatives, including spirovinylcyclopropane oxindoles, providing access to structurally diverse BCHeps with potential applications in drug discovery. The practicality of this method is demonstrated through scale-up reactions and downstream transformations of the cycloadducts.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"48 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866795","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}

{"title":"Enantioselective Synthesis of Chiral Seven-Membered Ring via Rh-Catalyzed 1,4-Addition of Arylboronic Acids to Enones","authors":"Ren-Rong Liu, Hao-Ran Wang, Wen-Guang Zhou, Li-Wen Zhan, Long-Long Xi","doi":"10.1039/d5qo00444f","DOIUrl":"https://doi.org/10.1039/d5qo00444f","url":null,"abstract":"A rhodium-catalyzed reaction between enones and arylboronic acids has been developed to construct chiral seven-membered ring through enantioselective 1,4-addition. This reaction offers outstanding functional group compatibility and excellent regio-, and enantiooselectivities using easily accessible arylboronic acids. Furthermore, to confirm the practicality of the reaction and understand its mechanism, we conducted in-depth studies on both product transformations and reaction pathways. This method demonstrates numerous advantages, including mild reaction conditions, readily available catalysts and ligands, a broad range of substrates, and the potential for synthesizing similar scaffolds of natural products.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862650","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}