Organic Chemistry Frontiers最新文献_第8页

meta-Selective thiofluoroalkylation of substituted pyridines via Zincke imines 通过锌克亚胺对取代的吡啶进行元选择性硫代氟烷基化反应

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-25 DOI: 10.1039/d5qo00533g

Will Connor Hartley, Arnau Huerta, Júlia C. Negredo, Omar Boutureira

引用次数: 0

Conformational Preference of N-Difluoromethylated Amides: Contributions of Hydrogen-Bonding, Steric, and Stereoelectronic Effects n-二氟甲基化酰胺的构象偏好：氢键、立体电子和立体电子效应的贡献

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-25 DOI: 10.1039/d5qo00497g

Ryu Yamasaki, Ami Tashiro, Chisaki Sato, Ai Ito, Iwao Okamoto

{"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 N-difluoromethylated amides and the effects of the difluoromethyl group, focusing on hydrogen-bonding, steric and stereoelectronic effects. N-Difluoromethylated amides were synthesized directly from amides using TMSCF2Br and tBuONa as a base. NMR analysis revealed that N-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 n(O) → π*C=O interaction play major roles in determining the conformational preferences. In addition, the trans conformer of the N-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}

引用次数: 0

Bis-Fischer Indole[3,2-b]carbazole Modification of [10]Cycloparaphenylenes: Tuning Optical Properties Through Rigid Substitution Bis-Fischer吲哚[3,2-b]咔唑改性[10]环对苯：通过刚性取代调整光学性质

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-24 DOI: 10.1039/d5qo00539f

Wanchun Duan, Dongming Chen, Dang Zhen, Shidong He, Wanqun Hu, Lu-Yuan Hao, Xin Xu

{"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}

引用次数: 0

Acidic pH Modulated Photoswitching of Sulfur-bridged Seven-membered Cyclic Azopyridines 酸性pH调制硫桥接七元环偶氮吡啶的光开关

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-24 DOI: 10.1039/d5qo00315f

Fengying Lan, Cefei Zhang, Zhihao Liu, Sitong Li, Jinmeng Yan, Xiaohu Zhao, Changwei Hu, Zhishan Su, Pengchi Deng, Zhipeng Yu

{"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[b,f][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[b]pyrido[f][1,4,5]thiadiazepines (BPTD) and dipyrido[2,3-b:3',2'-f][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[b]pyrido[3,4-f][1,4,5]thiadiazepine (3-BPTD) exhibits slightly enhanced photoswitching amplitude (photostationary distribution of E-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}

引用次数: 0

Chiral phosphoric acid catalyzed asymmetric synthesis of C−N axially chiral uracils with antitumor activity through kinetic resolution strategy 手性磷酸通过动力学分解催化不对称合成具有抗肿瘤活性的C−N轴手性尿嘧啶

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-24 DOI: 10.1039/d5qo00144g

Jiawei Xu, Haisong Xu, Yunyi Xu, Zhong-Qi Peng, Wei Zhang, Xin Li

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Palladium-catalyzed double strain-release (3+3) cycloaddition for the synthesis of vinylbicyclo[3.1.1]heptanes 钯催化双应变释放 (3+3) 环加成法合成乙烯基双环[3.1.1]庚烷

IF 5.4 1区化学

Organic Chemistry Frontiers Pub Date : 2025-04-24 DOI: 10.1039/d5qo00460h

Xin-Yu Gao, Yuanjiu Xiao, Xuan Zhan, Yu-Jie Li, Kun-Ju Wang, Jian-Jun Feng

引用次数: 0

Enantioselective Synthesis of Chiral Seven-Membered Ring via Rh-Catalyzed 1,4-Addition of Arylboronic Acids to Enones 铑催化1,4-芳基硼酸加成烯酮手性七元环的对映选择性合成