Chinese Journal of Chemistry最新文献

{"title":"Energy Transfer-Mediated, Triplet Excited State Proton Transfer-Enabled Dearomatization of Indole Derivatives with Amide Functionalities","authors":"Li Yang,&nbsp;Yi Pan,&nbsp;Peng Zhang,&nbsp;Liping Shi,&nbsp;Sheng Huang,&nbsp;Yijing Shu,&nbsp;Zhijie Zhang,&nbsp;Yimou Gong,&nbsp;Li Wang,&nbsp;Kai-Chung Lau,&nbsp;Qiang Fu","doi":"10.1002/cjoc.202401146","DOIUrl":"https://doi.org/10.1002/cjoc.202401146","url":null,"abstract":"<div>\u0000 \u0000 <p>The dearomatization of indole derivatives bearing amide functionalities presents a significant challenge due to the inherent stability of the amide carbonyl group, resulting from nitrogen lone-pair delocalization that imparts increased resonance stabilization. In this study, we report a visible-light photocatalytic intramolecular dearomatization of indole derivatives with amide groups, achieving the synthesis of spiroindolines <i>via</i> energy transfer. This method enables the efficient formation of a range of hydroxyl-substituted spiroindolines in moderate to high yields, with excellent diastereoselectivity (&gt; 20 : 1) under mild reaction conditions. Control experiments confirmed the involvement of an energy transfer pathway in the reaction mechanism. Density Functional Theory (DFT) calculations further revealed π-π stacking interactions between the indole core and pyridine ring, along with the strengthening of hydrogen bonding between the pyridine nitrogen and hexafluoroisopropanol (HFIP) in the excited state. These interactions facilitated the energy transfer-mediated triplet excited state intermolecular proton transfer (T-ESPT), crucial for activating the otherwise amide functionality. This protocol represents a rare example of harnessing the reactivity of amide groups for dearomative transformations.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1129-1134"},"PeriodicalIF":5.5,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836370","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":"Dual Cu/Ir Catalyzed Asymmetric Allylation and Pictet-Spengler Cyclization: Stereodivergent Access to Chiral Indole Fused 9-Azabicyclo[4.2.1]nonanes†","authors":"Xin-Lian Liu,&nbsp;Lu Xiao,&nbsp;Yi Liu,&nbsp;Yan Li,&nbsp;Zuo-Fei Wang,&nbsp;Xin Chang,&nbsp;Xiu-Qin Dong,&nbsp;Chun-Jiang Wang","doi":"10.1002/cjoc.202500016","DOIUrl":"https://doi.org/10.1002/cjoc.202500016","url":null,"abstract":"<div>\u0000 \u0000 <p>Nitrogen-containing bridged-heterocycles and indoles are key subunits of many natural products and pharmacologically active molecules. We herein present a bimetallic Cu/Ir catalyzed asymmetric allylation of ketimine esters and (<i>E</i>)-4-indolyl allyl carbonates followed by acid-promoted Pictet-Spengler cyclization sequences, enabling stereodivergent synthesis of chiral indole fused 9-azabicyclo[4.2.1]nonanes containing an eight-membered ring with one tertiary and two quaternary stereogenic centers. This one-pot sequential protocol features step economy, good substrate tolerance, and excellent stereoselective control.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1223-1229"},"PeriodicalIF":5.5,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897162","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":"Computation-Guided Regulation of Thiophene-Based Covalent Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution†","authors":"Xiao Luo,&nbsp;Yuxiang Chen,&nbsp;Jia-Tong Lin,&nbsp;Jie Luo,&nbsp;Ri-Qin Xia,&nbsp;Na Yin,&nbsp;Yang-Min Lin,&nbsp;Haiyan Duan,&nbsp;Shi-Bin Ren,&nbsp;Qiang Gao,&nbsp;Guo-Hong Ning,&nbsp;Dan Li","doi":"10.1002/cjoc.202401245","DOIUrl":"https://doi.org/10.1002/cjoc.202401245","url":null,"abstract":"<div>\u0000 \u0000 <p>Compared to the conventional trial-and-error approach, computational prediction is becoming an increasingly prominent approach in the discovery of covalent organic frameworks (COFs) with specific applications, yet it has been rarely demonstrated. Herein, we employed density functional theory (DFT) to pre-screen the electronic and optical properties of thiophene-based donor-acceptor (D-A) pairs simplified from their corresponding COF structures. Theoretical calculation illustrates the <b>BMTB-BTTC</b> with the highest number of thiophene units is expected to exhibit the best photocatalytic performance for hydrogen production. According to calculation prediction, four COFs have been prepared and their photocatalytic activities have been experimentally validated. Interestingly, the corresponding <b>BMTB-BTTC-COF</b> shows the highest photocatalytic hydrogen production rate of 12.37 mmol·g^–1·h^–1 among the four COFs. Combining the calculation and experimental results, it has been proven that the photocatalytic activity can be fine-tuned by modulating the number of thiophene units. Our study provides a new strategy for the rational design and regulation of D-A COFs to enhance photocatalytic activity through computational prediction.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1199-1207"},"PeriodicalIF":5.5,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836439","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":"Multi-modal Homogeneous Chemical Reaction Performance Prediction with Graph and Chemical Language Information","authors":"Shen Wang,&nbsp;Weiren Zhao,&nbsp;Yining Liu,&nbsp;Yang Li","doi":"10.1002/cjoc.202401186","DOIUrl":"https://doi.org/10.1002/cjoc.202401186","url":null,"abstract":"<div>\u0000 \u0000 <p>Accurate prediction for chemical reaction performance offers optimal direction for synthetic development. To this end, we present a novel multi-modal model called MMHRP-GCL to achieve the prediction of homogeneous chemical reaction yield, enantioselectivity, and activation energy by fusing the information from the text and graph modalities, requiring only 8 simple descriptors and Reaction SMILES obtained without high-cost DFT computation, and capable of managing reactions involving a fluctuating number of molecules. Experimental results on 4 datasets show that MMHRP-GCL outperforms at least 7 generalized SOTA methods. Ablation study confirms the critical roles of the complementation of graph and text modalities, as well as the significance of modality alignment and atomic features in prediction. Albeit there is still room for improvement in the interpretation of atomic relationships, the model has a remarkable ability to identify important atoms. A statistically interpretable study of the feature importance and a test on challenging dataset further demonstrates the utility and potential of the model. As a high-accuracy, low-cost, interpretable, and general multi-modal model, MMHRP-GCL provides valuable guidance on the design of forward predictors for homogeneous catalytic reactions.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1230-1238"},"PeriodicalIF":5.5,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897095","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":"Selective Recognition of Nucleoside Triphosphates in Water by Tetraphenylethene-Based Tetraimidazolium Cyclophanes†","authors":"Pingxia Wang,&nbsp;Yingjie Li,&nbsp;Lingyu Zhao,&nbsp;Yanxia Yang,&nbsp;Xuhao Kang,&nbsp;Ting Yang,&nbsp;Fan Cao,&nbsp;Lin Cheng,&nbsp;Liping Cao","doi":"10.1002/cjoc.202401247","DOIUrl":"https://doi.org/10.1002/cjoc.202401247","url":null,"abstract":"<div>\u0000 \u0000 <p>The design and development of selective recognition and sensing systems for biologically important nucleoside triphosphates (NTPs) have attracted significant attention in recent years, owing to their critical roles in cellular processes. In this study, we report the synthesis of two tetraphenylethene-based tetraimidazolium cyclophanes (<b>1</b> and <b>2</b>) through a one-step S_N2 reaction. These cyclophanes are capable of recognizing NTPs by forming stable 1 : 1 host-guest complexes in aqueous solution. Of particular interest, cyclophane <b>1</b> demonstrates exceptional selectivity for guanosine triphosphate (GTP), distinguishing it from other nucleoside triphosphates such as ATP, CTP, and UTP. This selective recognition is accompanied by distinct and measurable fluorescence responses, which are significantly enhanced upon binding to GTP, enabling the potential for sensitive detection. This study highlights the potential of tetraphenylethene-based tetraimidazolium cyclophanes as a highly selective and sensitive sensor for GTP, offering new insights into the design of molecular systems for the recognition of biologically relevant nucleotides.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1173-1180"},"PeriodicalIF":5.5,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836258","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 Porous Frameworks for Enantioselective Separation and Asymmetric Catalysis","authors":"Bing Yan,&nbsp;Jin-Hui Song,&nbsp;Da-Long Zhang,&nbsp;Zong-Jie Guan,&nbsp;Yu Fang","doi":"10.1002/cjoc.202401094","DOIUrl":"https://doi.org/10.1002/cjoc.202401094","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <p>The preparation and resolution of chiral molecules hold significant importance in scientific and industrial domains, such as drug development and manufacturing. In recent years, chiral porous frameworks have attracted increasing attention in asymmetric catalysis and enantiomer resolution due to their excellent performance. The metal-organic frameworks (MOFs), covalent organic frameworks (COFs), porous organic cages (POCs), and porous coordination cages (PCCs) are important representative of the porous framework family. Significantly, chirality can be easily introduced into these framework materials through simple bottom-up or post-modification methods, thereby promoting their applications related to chirality. In this review, we systematically summarize the synthesis strategies of four classes of chiral framework materials and their applications in asymmetric catalysis and enantiomeric resolution. Finally, we present some perspectives on the future development in chiral porous frameworks.</p>\u0000 \u0000 <p>\u0000 </p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Key Scientists</h3>\u0000 \u0000 <p>Significant progress has been made in the development of chiral porous frameworks, primarily driven by the application of chiral molecules. This area of research has seen contributions from many distinguished scientists. A particularly important milestone was reached in 2000, when Kimoon Kim reported the first catalytic Chiral Metal-Organic Framework (CMOF). In 2001, Lin <i>et al</i>. reported a new generation of recyclable CMOF capable of chiral separation and heterogeneous catalysis. Simultaneously, researchers such as Cui and Duan have made substantial contributions, advancing the field considerably. Furthermore, notable developments have been made in the area of Chiral Covalent Organic Frameworks (CCOFs), with pioneering work by researchers like Jiang, Wang, and Cui. Meanwhile, some groups such as Su and Li have made significant strides in the chiral cages. These remarkable accomplishments have drawn considerable interest.</p>\u0000 \u0000 <p></p>\u0000 </section>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 9","pages":"1078-1089"},"PeriodicalIF":5.5,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143749913","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 Tandem Route toward Isoxazolidine Fused Phospholene Skeleton Involving Dearomative [3+2] Cycloaddition of P-Heteroarenes and Nitrones","authors":"Chenyong Xu,&nbsp;Yingqiang Wang,&nbsp;Meng Xiao,&nbsp;Rongqiang Tian,&nbsp;Zheng Duan","doi":"10.1002/cjoc.202401319","DOIUrl":"https://doi.org/10.1002/cjoc.202401319","url":null,"abstract":"<div>\u0000 \u0000 <p>The demands for effective assembly of structurally complex molecular scaffolds from simple starting materials are continuously growing along with the development of organic chemistry. We have developed a tandem approach that assembles simple <i>β</i>-chloroethylphosphane, alkynyl imines (or alkynyl ketones), and nitrones into structurally complex isoxazolidine fused phospholene scaffolds through a sequential process involving phospha-Michael addition, intramolecular cyclization, and dearomatizing [3+2] cycloaddition reactions. The isoxazolidine-fused phospholene has three heteroatoms, including a junction phosphorus atom. After removing the coordinated tungsten group, these compounds can serve as potential P-stereogenic ligands and may have biological activities. Contrary to pyrroles and furans, the aromatic 2-phosphapyrroles and 2-phosphafurans are good 2π-electron candidates in the dearomative [3+2] cycloaddition reactions due to the poor overlap of the 2p-3p orbitals of the C=P moiety.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1161-1166"},"PeriodicalIF":5.5,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836358","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":"Weak Absorptive Component Boosts Exciton Dissociation in Indoor Organic Photovoltaics","authors":"Zhenchuan Wen,&nbsp;Jiawei Qiao,&nbsp;Yuying Yang,&nbsp;Xiaotao Hao","doi":"10.1002/cjoc.202401167","DOIUrl":"https://doi.org/10.1002/cjoc.202401167","url":null,"abstract":"<div>\u0000 \u0000 <p>Indoor organic photovoltaic (OPV) cells have emerged as promising candidates for harvesting energy from artificial light sources. However, the limited spectral range and low photon flux of indoor light sources restrict the photocurrent and power output of these devices. In this work, we investigate the role of a weak absorptive third component in enhancing exciton dissociation and improving indoor OPV performance. By introducing eC9-2Cl into a D18-Cl:F-BTA3 binary system, we create a ternary blend that demonstrates significant improvements in device efficiency. Transient absorption spectroscopy and time-resolved photoluminescence measurements reveal that eC9-2Cl facilitates efficient energy transfer and exciton dissociation. Under indoor lighting conditions, where eC9-2Cl acts as a weak absorptive third component, the ternary devices exhibit a power conversion efficiency increase from 24.7% to 26.2%. These findings highlight the potential of weak absorptive components in optimizing energy transfer processes and overcoming the limitations of indoor light harvesting in OPV systems.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1148-1154"},"PeriodicalIF":5.5,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836321","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 General Approach for Fluoroalkylation of O-Nucleophiles with Monofluoroalkylated Sulfonium Ylides†","authors":"Yisa Xiao,&nbsp;Qilong Shen","doi":"10.1002/cjoc.202500001","DOIUrl":"https://doi.org/10.1002/cjoc.202500001","url":null,"abstract":"<div>\u0000 \u0000 <p>The development of a series of shelf-stable monofluoroalkylated sulfonium ylide reagents and their reactions with a variety of <i>O</i>-nucleophiles including phenols, sulfonic acids, carboxylic acids, 1-hydroxy-benzotrizoles, amino acids was described. In general, monofluoroakylated sulfonium ylides were synthesized in three steps from commercially available starting materials including thiophenols, alkyl halides and dimethyl 2-diazomalonate. Reactions with the <i>O</i>-nucleophiles occurred under mild conditions and afforded the corresponding monofluoroalkylated ethers, sulfonates, and esters in good to excellent yields, thus providing a robust approach for the preparation of these compounds. Further expansion of monofluoroalkylation of C-terminus of peptides potentially provided modified drug-like peptides.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1114-1120"},"PeriodicalIF":5.5,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836322","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":"Selective Synthesis of Bromo-substituted 2H-Pyrroles and 3H-Pyrroles via Three-Component Cascade Annulation of 1,3-Enynes, NBS and TMSN3","authors":"Zhen Zhang,&nbsp;Qingting Song,&nbsp;Fan Qin,&nbsp;Han Yue,&nbsp;Xiaoyu Xie,&nbsp;Lei Wang,&nbsp;Tao Miao","doi":"10.1002/cjoc.202401260","DOIUrl":"https://doi.org/10.1002/cjoc.202401260","url":null,"abstract":"<div>\u0000 \u0000 <p>A novel and efficient method for selective synthesis of bromo-substituted 2<i>H</i>-pyrroles and 3<i>H</i>-pyrroles has been achieved from 1,3-enynes, NBS and TMSN₃ <i>via</i> H₂O-promoted cyclization reactions or TFA-catalyzed cyclization/2,3-shift reactions, providing a range of structurally diverse products in moderate to good yields under mild conditions.</p>\u0000 <p></p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1155-1160"},"PeriodicalIF":5.5,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836359","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}