Yan-E Zhang , Yingtao Jiang , Yun Zhang , Hu Wang , Zitong Wu , Rui Li , Yumiao Ma , Tao Tu
{"title":"Enantioselective synthesis of bulky planar-chiral pillar[n]arenes through dynamic kinetic resolution","authors":"Yan-E Zhang , Yingtao Jiang , Yun Zhang , Hu Wang , Zitong Wu , Rui Li , Yumiao Ma , Tao Tu","doi":"10.1016/j.cclet.2025.111201","DOIUrl":"10.1016/j.cclet.2025.111201","url":null,"abstract":"<div><div>The precise synthesis of planar chiral pillar[<em>n</em>]arenes (PAs) faces significant challenges due to their inherent dynamic racemization induced by rapid molecular flipping. To address this issue and enhance conformational stability of these macrocycles, we have developed a strategic approach involving the introduction of sterically bulky aryl (sp<sup>2</sup>) substituents at the molecular rims through dynamic kinetic resolution (DKR). A series of robust and chirality-aligned homo- and hetero-diaryl PAs (<em>n</em> = 5, 6) were achieved with excellent enantioselectivity (>95 % <em>ee</em>) <em>via</em> Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions. Mechanism study revealed axial steric hindrance, rather than radial substitution, governs conformational chirality-locking in pillar[<em>n</em>]arenes. This work not only provides an attractive protocol for the enantioselective synthesis of planar chiral pillar[<em>n</em>]arenes, but also enriches the library of macrocycles for promising applications in chiral molecular machines, enantioselective sensors, and chiral luminescent materials.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 12","pages":"Article 111201"},"PeriodicalIF":8.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145107644","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}
Hanqi Zhang , Biao Gao , Yuanyuan Feng , Guijuan Zheng , Zhijun Liu , Lichun Kong , Junjun Liu , Haji Akber Aisa , Guangmin Yao
{"title":"DFT calculations and dynamic NMR revealed the coalescent NMR phenomena of the 6/6/6/9 tetracyclic merosesquiterpenoids with an unprecedented 9,15-dioxatetracyclo[8.5.3.04,17.014,18]octadecane core skeleton","authors":"Hanqi Zhang , Biao Gao , Yuanyuan Feng , Guijuan Zheng , Zhijun Liu , Lichun Kong , Junjun Liu , Haji Akber Aisa , Guangmin Yao","doi":"10.1016/j.cclet.2025.111234","DOIUrl":"10.1016/j.cclet.2025.111234","url":null,"abstract":"<div><div>Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers, dauroxonanols A (<strong>1</strong>) and B (<strong>2</strong>), possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.0<sup>4,17</sup>.0<sup>14,18</sup>]octadecane core skeleton, were isolated from <em>Rhododendron dauricum</em>. The nuclear magnetic resonance (NMR) spectra of <strong>1</strong> and <strong>2</strong> showed very broad resonances, and <sup>13</sup>C NMR spectrum of <strong>1</strong> exhibited only 13 instead of 22 carbon resonances. These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis. Their structures and absolute configurations of <strong>1</strong> and <strong>2</strong> were finally determined by single crystal X-ray diffraction analysis, chiral separation, and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for <strong>1</strong> and <strong>2</strong> are proposed. Conformational analysis, density functional theory (DFT) calculations, and dynamic NMR assigned the coalescent NMR phenomena of <strong>1</strong> and <strong>2</strong> to the conformational changes of the flexible oxonane ring. Dauroxonanols A (<strong>1</strong>) and B (<strong>2</strong>) showed potent α-glucosidase inhibitory activities, 2–8 times potent than acarbose, an antidiabetic drug targeting α-glucosidase in clinic.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 111234"},"PeriodicalIF":9.4,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144571536","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}
Yunzhe Du , Siliu Cheng , Shuyi Li , Junping Niu , Yuan Gou , Ligang Yan , Tian-Xing Zhang , Ruijun Xie , Limin Han , Tiezheng Jia , Ning Zhu
{"title":"C2-Transformation of calcium carbide trigered by hydrogen sulfide","authors":"Yunzhe Du , Siliu Cheng , Shuyi Li , Junping Niu , Yuan Gou , Ligang Yan , Tian-Xing Zhang , Ruijun Xie , Limin Han , Tiezheng Jia , Ning Zhu","doi":"10.1016/j.cclet.2025.111233","DOIUrl":"10.1016/j.cclet.2025.111233","url":null,"abstract":"<div><div>Calcium carbide, a bulky and cheap raw chemical, is traditionally depolymerized by water to release acetylene, allowing the downstream organic transformation. In this study, hydrogen sulfide (H<sub>2</sub>S), an industrial waste gas, has been exploited to depolymerize calcium carbide, which represents a strategy for the comprehensive utilization of both hydrogen sulfide and calcium carbide. As a proof of concept, a three-component condensation reaction was established to prepare thioamides directly from hydrogen sulfide and calcium carbide in high yields. Leveraging the unique properties of thioamides that possess both nucleophilic sulfur and electrophilic carbon sites, a series of novel tandem reactions were further developed to construct structurally diverse heterocyclic compounds. Our strategy not only provides a new chemical pathway for calcium carbide depolymerization, but also offers a solution for the utilization of hazardous hydrogen sulfide gas. More importantly, this approach facilitates the comprehensive and sustainable utilization of the calcium carbide resource.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 12","pages":"Article 111233"},"PeriodicalIF":8.9,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263662","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}
Xiaojun Wang , Yizhou Zhang , Linwei Guo , Jianwei Li , Peng Wang , Lei Yang , Zhiming Liu
{"title":"V2CTX MXene-derived ammonium vanadate with robust carbon skeleton for superior rate aqueous zinc-ion batteries","authors":"Xiaojun Wang , Yizhou Zhang , Linwei Guo , Jianwei Li , Peng Wang , Lei Yang , Zhiming Liu","doi":"10.1016/j.cclet.2025.111231","DOIUrl":"10.1016/j.cclet.2025.111231","url":null,"abstract":"<div><div>Layered ammonium vanadate has become a promising cathode material for aqueous zinc ion batteries (ZIBs) due to its small mass and large ionic radius of ammonium ions as well as the consequent large layer spacing and high specific capacity. However, the irreversible de-ammoniation caused by N·H···O bonds damaged would impair cycle life of ZIBs and the strong electrostatic interaction between Zn<sup>2+</sup> and V-O frame could slower the mobility of Zn<sup>2+</sup>. Furthermore, the thermal instability of ammonium vanadate also limits the use of common carbon coating modification method to solve the problem. Herein, V<sub>2</sub>CT<sub>X</sub> MXene was innovatively selected as a bifunctional source to <em>in-situ</em> derivatized (NH<sub>4</sub>)<sub>2</sub>V<sub>8</sub>O<sub>20</sub>·xH<sub>2</sub>O with amorphous carbon-coated (NHVO@C) <em>via</em> one-step hydrothermal method in relatively moderate temperature. The amorphous carbon shell derived from the V<sub>2</sub>CT<sub>X</sub> MXene as a conductive framework to effectively improve the diffusion kinetics of Zn<sup>2+</sup> and the robust carbon skeleton could alleviate the ammonium dissolution during long-term cycling. As a result, zinc ion batteries using NHVO@C as cathode exhibit superior electrochemical performance. Moreover, the assembled foldable or high loading (10.2 mg/cm<sup>2</sup>) soft-packed ZIBs further demonstrates its practical application. This study provided new insights into the development of the carbon cladding process for thermally unstable materials in moderate temperatures.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 8","pages":"Article 111231"},"PeriodicalIF":9.4,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144280510","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}
Sadia Rani , Najoua Sbei , Seyfeddine Rahali , Samina Aslam , Tomas Hardwick , Nisar Ahmed
{"title":"Electrochemical synthesis: A green & powerful approach to modern organic synthesis and future directions","authors":"Sadia Rani , Najoua Sbei , Seyfeddine Rahali , Samina Aslam , Tomas Hardwick , Nisar Ahmed","doi":"10.1016/j.cclet.2025.111216","DOIUrl":"10.1016/j.cclet.2025.111216","url":null,"abstract":"<div><div>Electrochemical synthesis is a safe, mild and environmentally friendly alternative to chemical oxidants and reductants. It uses electricity to catalyze redox reactions. However, understanding the tools and techniques involved is crucial for maximizing its benefits in academic and industrial applications. Still, for a novice, electrosynthesis can be a somewhat intimidating. Therefore, we provide guidance to synthetic chemists by highlighting key concepts and offering practical tips. In this review article, we focus on the utilization of electro-auxiliaries, indirect electrosynthesis, alternating electrode electrolysis (AEE), microreactors for electrochemical processes, and paired electrochemical reactions. These strategies are illustrated with selected examples. The use of electrodes and electroanalytical methods such as cyclic voltammetry are discussed. It highlights the advantages of merging electrochemistry and photochemistry, and the challenges of specific organic solvents and electrolytes. The incorporation of electrochemistry into a continuous chemical flow system further advances green activation technologies in terms of efficiency, applicability, sustainability, and selectivity to deliver more efficient and cleaner synthetic processes. Furthermore, this manuscript also emphasizes improvements in current approaches and future directions for large-scale electrosynthesis.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 11","pages":"Article 111216"},"PeriodicalIF":8.9,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144841238","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":"Synthetic application of oxalate salts for visible-light-induced radical transformations","authors":"Hui-Xian Jiang , Zhi-Tao Liu , Pei Xu, Xu Zhu","doi":"10.1016/j.cclet.2025.111224","DOIUrl":"10.1016/j.cclet.2025.111224","url":null,"abstract":"<div><div>Oxalic acid salts (oxalate) were recently developed as C1 synthon, potent single-electron-transfer (SET) reductant, and hole scavengers <em>via</em> generation of CO<sub>2</sub> and CO<sub>2</sub> radical anion (CO<sub>2</sub><sup>•−</sup>) under mild photochemical conditions. A series of challenging reductive transformations were realized with oxalic dianion under catalytic photoredox conditions or through an electron-donor-acceptor (EDA) complex formation process. As a chemical intermediate for carbon capture and utilization (also a cheap and readily available reagent), oxalate salts could release one electron easily (<em>E</em><sub>ox</sub> = +0.06 V <em>vs.</em> SCE) <em>via</em> visible-light irradiation to give CO<sub>2</sub> and CO<sub>2</sub><sup>•−</sup> and therefore opened a new arena for reductive carboxylation reactions with highly expanded reaction diversity and chemical space to realize challenging C-X bond activation, alkenes cross coupling, and reductive carboxylation of unsaturated chemical bonds in a more sustainable and efficient way. This review features the recently developed aspects with oxalate salts and also an outlook for its further application in organic radical transformations.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 12","pages":"Article 111224"},"PeriodicalIF":8.9,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145107642","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":"AL5E: A breakthrough in broad-spectrum coronavirus inactivation through structure-guided design","authors":"Heng Gao, Jiwei Zhang, Peng Zhan, Xinyong Liu","doi":"10.1016/j.cclet.2025.111221","DOIUrl":"10.1016/j.cclet.2025.111221","url":null,"abstract":"","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 7","pages":"Article 111221"},"PeriodicalIF":9.4,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143923652","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":"Site-specific surface amination strategy facilitates biomimetic encapsulation of enzymes within hydrogen-bonded organic framework","authors":"Haoquan Huang , Haiting Chen , Xinran Dong , Yanbin Xu , Anlian Huang , Qiaoyi Cen , Huairou Zhu , Guosheng Chen , Wei Yi , Siming Huang , Gangfeng Ouyang","doi":"10.1016/j.cclet.2025.111223","DOIUrl":"10.1016/j.cclet.2025.111223","url":null,"abstract":"<div><div>Hydrogen-bonded framework (HOF) offers an attractive platform to encapsulate enzymes and stabilize their conformation, due to the advantages of mild synthesis conditions, tailorable pore structure, and backbone biocompatibility. However, the efficiency of this HOF approach relies on the interfacial interactions between enzyme guest and the ligand precursors, limiting its adaptability to enzymes with varying surface chemistry property. In this study, we report a site-specific surface modification strategy to positively tailor the enzyme surface charge, facilitating the biomimetic encapsulation of enzymes within HOF <em>in situ</em>. Both experimental results and computational simulation reveal that site-specific amination of enzyme surface’s acidic residues contributes to the interfacial accumulation of carboxylic ligand precursors in aqueous solutions <em>via</em> synergistic electrostatic and hydrogen bonding interactions. This substantially facilitates the <em>in situ</em> growth of porous HOF surrounding the aminated enzyme biotemplates, with up to 100 % enzyme loading efficiency. The resultant hydrogen-bonded biohybrid framework (HBF) retains high biocatalytic functions while exhibiting exceptional stability under harsh conditions. By leveraging the marked catalytic activity of GOx-NH<sub>2</sub>@HBF-1 and a H<sub>2</sub>O<sub>2</sub>-sensitive QD, a highly sensitive glucose fluorescence sensor is fabricated with a wide linear range (5–2000 µmol/L) and a low quantification limit of 5 µmol/L. This work presents a simple yet effective enzyme surface engineering approach for integrating enzyme into HOF, opening new avenues for the construction of multifunctional HOF biocomposites.</div></div>","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 9","pages":"Article 111223"},"PeriodicalIF":9.4,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144587848","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}
Yi-Kao Xu , Guo-Ping Luo , Liang-Bin Hu , Wei-Min He
{"title":"Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes","authors":"Yi-Kao Xu , Guo-Ping Luo , Liang-Bin Hu , Wei-Min He","doi":"10.1016/j.cclet.2025.111226","DOIUrl":"10.1016/j.cclet.2025.111226","url":null,"abstract":"","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 8","pages":"Article 111226"},"PeriodicalIF":9.4,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144169196","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}
Shenghui Tu , Anru Liu , Hongxiang Zhang , Lu Sun , Minghui Luo , Shan Huang , Ting Huang , Honggen Peng
{"title":"Corrigendum to “Oxygen vacancy regulating transition mode of MIL-125 to facilitate singlet oxygen generation for photocatalytic degradation of antibiotics” [Chinese Chemical Letters 35 (2024) 109761]","authors":"Shenghui Tu , Anru Liu , Hongxiang Zhang , Lu Sun , Minghui Luo , Shan Huang , Ting Huang , Honggen Peng","doi":"10.1016/j.cclet.2025.110868","DOIUrl":"10.1016/j.cclet.2025.110868","url":null,"abstract":"","PeriodicalId":10088,"journal":{"name":"Chinese Chemical Letters","volume":"36 6","pages":"Article 110868"},"PeriodicalIF":9.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143830255","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}