Chemical Science最新文献_第7页

Oxygen-responsive high-efficiency orange-red room-temperature phosphorescence from chalcogen-containing dibenzo[a,c]phenazine foldamers. 含硫二苯并[a，c]非那嗪文件夹体的氧响应型高效橙红色室温磷光。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-08 DOI: 10.1039/d6sc06201f

Fuying Zhao, Zhiqiang Yang, Yating Wen, Jiatuo Zhang, Ruichun Gu, Hanbing He, Ximing Dong, Xiaoyang Fan, Haichao Liu, Bing Yang

{"title":"Oxygen-responsive high-efficiency orange-red room-temperature phosphorescence from chalcogen-containing dibenzo[a,c]phenazine foldamers.","authors":"Fuying Zhao, Zhiqiang Yang, Yating Wen, Jiatuo Zhang, Ruichun Gu, Hanbing He, Ximing Dong, Xiaoyang Fan, Haichao Liu, Bing Yang","doi":"10.1039/d6sc06201f","DOIUrl":"10.1039/d6sc06201f","url":null,"abstract":"Efficient orange-red/red room-temperature phosphorescence (RTP) in purely organic materials is highly desirable for bio-imaging and information security but remains scarce due to the energy gap law and the challenge in achieving strong spin-orbit coupling (SOC) in red-emitting systems. Herein, a functional unit combination strategy was employed to develop a series of orange-red-emitting RTP materials. By modifying a dibenzo[a,c]phenazine (DBP) emissive core with flexible chalcogen-containing foldamers (phenylselenyl, phenylthio, or phenoxyl), three new compounds (O-DBP, S-DBP, and Se-DBP) were synthesized. While the DBP core governs the triplet energy level and emission color, the varied chalcogen-containing foldamers significantly modulate the phosphorescence efficiency. Notably, Se-DBP achieves orange-red RTP peaking at 630 nm with a phosphorescence quantum yield of 33.04% in doped PMMA films. Our findings reveal that the superior performance of Se-DBP originates from enhanced SOC driven by the synergy between the heavy-atom effect and n/π orbital decoupling mechanism in the phenylselenyl-containing foldamer. Furthermore, these materials exhibit unique oxygen-sensitive RTP properties, which enable potential applications in anti-counterfeiting and encryption, ratiometric oxygen sensing, and cellular hypoxia imaging. This work not only validates the effectiveness of the functional unit combination strategy for developing high-efficiency orange-red/red RTP materials, but also expands their applicability across diverse fields.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13669857/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149214990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Partial ligand exchange on CsPbI₃ nanocrystals with alkyl phosphonium iodide improves phase stability and emission efficiency in light-emitting diodes. CsPbI3纳米晶体与烷基碘化磷的部分配体交换提高了发光二极管的相稳定性和发射效率。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc06271g

Shence Zhang, Meenakshi Pegu, Luca Goldoni, Hossein Roshan, Umberto Filippi, Abdessamad El Adel, Francesco De Boni, Simone Lauciello, Zhanzhao Li, Yuting Song, Ivan Infante, Francesco Di Stasio, Liberato Manna

{"title":"Partial ligand exchange on CsPbI3 nanocrystals with alkyl phosphonium iodide improves phase stability and emission efficiency in light-emitting diodes.","authors":"Shence Zhang, Meenakshi Pegu, Luca Goldoni, Hossein Roshan, Umberto Filippi, Abdessamad El Adel, Francesco De Boni, Simone Lauciello, Zhanzhao Li, Yuting Song, Ivan Infante, Francesco Di Stasio, Liberato Manna","doi":"10.1039/d6sc06271g","DOIUrl":"10.1039/d6sc06271g","url":null,"abstract":"All-inorganic colloidal CsPbI3 nanocrystals are promising materials for light-emitting applications owing to their excellent optoelectronic properties. However, their practical implementation remains limited by surface defects, ligand instability, and phase degradation under ambient conditions. Here, we employ trimethyl(dodecyl)phosphonium iodide (TDP-I) as a post-synthetic ligand for partial ligand exchange on CsPbI3 nanocrystals initially coated with a ligand shell that is primarily composed of oleylammonium ions. X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and nuclear magnetic resonance analyses confirm that TDP-I is only partially replacing the native ligand shell. These findings are in line with classical molecular dynamics calculations, which indicate that a mixed oleylammonium/TDP+ ligand shell is more stable than a full TDP+ one. The TDP-I treatment improved photophysical properties including an increase in the photoluminescence quantum yield (from ∼77% to ∼90%), accompanied by prolonged photoluminescence lifetime and reduced nonradiative recombination. The TDP-I-treated nanocrystals also exhibit improved stability, with delayed transformation from the orthorhombic phase to the non-perovskite δ-phase under ambient conditions. When incorporated into light-emitting diodes, the TDP-I-treated CsPbI3 nanocrystals deliver a maximum external quantum efficiency of 12.4%. These results demonstrate that partial phosphonium ligand exchange provides an effective strategy for optimizing the surface chemistry, optical properties, and device performance of CsPbI3 nanocrystals, highlighting the importance of mixed-ligand surface engineering for perovskite optoelectronics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13644397/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149135173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

DNA-scaffolded catalysis for aliphatic alcohol oxidation in DEL synthesis. dna支架催化DEL合成中脂肪醇氧化。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc05041g

Ethan M Hartman, Jeffrey D Martell

{"title":"DNA-scaffolded catalysis for aliphatic alcohol oxidation in DEL synthesis.","authors":"Ethan M Hartman, Jeffrey D Martell","doi":"10.1039/d6sc05041g","DOIUrl":"10.1039/d6sc05041g","url":null,"abstract":"Compared to traditional methods for screening small molecule drug candidates, DNA-encoded libraries (DELs) offer greatly increased throughput by tethering each small molecule to unique DNA barcodes, allowing simultaneous screening of billions of small molecules in a single test-tube. Impressive advances have been made in adapting traditional organic reactions to be DNA-compatible, allowing for the synthesis of DELs with ever-expanding chemical diversity. Nonetheless, DNA is a fragile molecule that is damaged by many chemical reaction conditions, making these conditions incompatible with DEL synthesis. The fragility of DNA therefore necessitates the development of new platforms to accelerate the desired transformation of the tethered small molecules while minimizing damage to the DNA barcodes. Here, we report a DNA-scaffolded catalysis platform for high-yielding, high-selectivity transformations in the construction of DELs under mild conditions. Through DNA-scaffolding, the catalyst is brought in proximity to DNA-tethered small molecules, lowering the catalyst concentration needed and minimizing off-target DNA damage. We demonstrate the platform in the context of aliphatic alcohol oxidation, a transformation for which conventional reactions with free-floating catalysts cause oxidative DNA damage. We further demonstrate that the DNA-scaffolded DEL synthesis platform can be incorporated into existing DEL synthesis workflows. We anticipate that the DNA-scaffolded DEL synthesis platform will find broad utility in improving the DNA-compatibility of organic transformations and will expand the toolkit of DNA-compatible chemical reactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13643529/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149135239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enantioselective synthesis of β-aryl-β-acyl esters as unsymmetrical 1,4-dicarbonyl compounds via oxidative aryl rearrangement using λ₃-perchrolate iodane. λ3-高氯酸碘通过氧化芳基重排对映选择性合成不对称1,4-二羰基化合物β-芳基-β-酰基酯。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc06374h

Honoka Kasahara, Yuna Nishiguchi, Katsuhiko Moriyama

{"title":"Enantioselective synthesis of β-aryl-β-acyl esters as unsymmetrical 1,4-dicarbonyl compounds via oxidative aryl rearrangement using λ3-perchrolate iodane.","authors":"Honoka Kasahara, Yuna Nishiguchi, Katsuhiko Moriyama","doi":"10.1039/d6sc06374h","DOIUrl":"https://doi.org/10.1039/d6sc06374h","url":null,"abstract":"In synthetic chemistry, structurally diverse unsymmetrical 1,4-dicarbonyl compounds are important, and general strategies for their asymmetric synthesis, particularly for β-aryl-substituted β-acyl esters, are scarce. Therefore, this study presents an enantioselective oxidative aryl rearrangement of α-styryl esters using a combination of a hypervalent iodine(iii) reagent and Mg(ClO4)2 as a Lewis acid to provide chiral β-aryl-β-formyl and β-aryl-β-acyl esters in high yields with excellent enantioselectivities. Mechanistic studies and density functional theory (DFT) calculations revealed that a µ-(oxo)diiodo-diphenyl diperchlorate species, generated in situ from ArI(OAc)2 and Mg(ClO4)2, promotes the aryl rearrangement with remarkable chemoselectivity toward the substrate functional groups. Divergent derivatizations of the resulting chiral unsymmetrical 1,4-dicarbonyl compounds, which furnished a variety of enantioenriched phenyl-substituted molecules, demonstrated the synthetic utility of the method.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13659808/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179632","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Base-catalyzed intramolecular C-H annulation reactions of o-carboranes containing nitriles, alkynes, and alkenes. 碱催化含腈、炔和烯烃的邻碳硼烷分子内碳氢环化反应。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc03717h

Hui Han, Yu-Wei Chen, Jing-Yi Zhang, Xin Li, Rui-Zeng Zhang, Man Zhang, Wen-Hao Li, Yan-Na Ma, Donghui Wei, Xuenian Chen

{"title":"Base-catalyzed intramolecular C-H annulation reactions of o-carboranes containing nitriles, alkynes, and alkenes.","authors":"Hui Han, Yu-Wei Chen, Jing-Yi Zhang, Xin Li, Rui-Zeng Zhang, Man Zhang, Wen-Hao Li, Yan-Na Ma, Donghui Wei, Xuenian Chen","doi":"10.1039/d6sc03717h","DOIUrl":"https://doi.org/10.1039/d6sc03717h","url":null,"abstract":"The C-H bonds of carboranes display acidity and can be functionalized under stoichiometric amounts of strong bases. However, the harsh reaction conditions lead to poor functional-group compatibility and cumbersome reaction handling. Herein, we achieved intramolecular C-H bond addition of o-carboranes to nitriles, unactivated alkynes, and alkenes using a catalytic alkoxide-mediated protocol for nitriles and a silylamide-promoted protocol for alkynes and alkenes at room temperature. Through this method, we synthesized a series of carborane-fused five- and six-membered compounds. Further deboronation afforded the corresponding five-membered carbocyclic fused nido-carboranes from arylnitrile-substituted o-carboranes, whereas those containing benzeneacetonitrile groups isomerize to six-membered fused carborane enamines. This protocol also enables intramolecular C-H annulation reactions with nonpolar alkynes and alkenes, leading to highly selective formation of five-membered E-olefinic carboranes and five-membered alkane-fused carboranes, respectively. Theoretical calculations reveal that the new fused five- and six-membered carbocycles exhibit small NICS values and thus cannot be considered weakly aromatic, indicating that leveraging the synergistic effects of electronic coupling and properties between the 3D carborane and the 2D polycyclic ring yields unique physicochemical properties. Moreover, the novel nido-carborane structures exhibit a distinct pH probe and a highly efficient yellow emitter, with a solid-state luminous efficiency of 42.5% obtained using this method.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13659815/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149179710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal-free CO₂ fixation: conversion of epoxides to cyclic carbonates by a highly efficient bifunctional boron-tethered N-heterocyclic nitrenium catalyst. 无金属二氧化碳固定：用高效双功能硼系n杂环氮催化剂将环氧化物转化为环状碳酸盐。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc05761f

Rahul Mondal, Reetu Rani Mondal, K Geetharani

引用次数: 0

Single-atom site modulation of Cu electrocatalysts for CO₂ electroreduction. Cu电催化剂在CO2电还原中的单原子位调制。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc06295d

Yaqian Li, Kaiwen Xing, Xiang Chen, Shuren Zhang, Xiao Liang, Ya-Hao Wang, Yadong Li

{"title":"Single-atom site modulation of Cu electrocatalysts for CO2 electroreduction.","authors":"Yaqian Li, Kaiwen Xing, Xiang Chen, Shuren Zhang, Xiao Liang, Ya-Hao Wang, Yadong Li","doi":"10.1039/d6sc06295d","DOIUrl":"10.1039/d6sc06295d","url":null,"abstract":"Copper is the only metal capable of efficiently converting CO2 into multi-carbon (C2+) products, yet its practical application is hindered by poor intrinsic selectivity, complex active sites, and limited pathway control. Single-atom site modified Cu catalysts (SAMCs) offer an effective strategy to overcome these challenges by introducing atomically dispersed heterometallic sites that retain the C-C coupling ability of Cu while precisely regulating CO2 activation, C-C coupling, and hydrogen-transfer kinetics through interfacial synergy. This review summarizes recent advances in SAMCs for CO2 electroreduction. We first introduce synthetic strategies for constructing isolated sites on Cu, including electrochemical reconstruction, electrodeposition, galvanic replacement, vacancy-mediated cation exchange, and co-reduction. We then discuss the mechanisms of single-atom regulation in CO2 activation, C-C coupling, and hydrogen transfer. Finally, we highlight emerging design principles, including the 10-electron counting rule, d-p orbital matching, and data-driven catalyst discovery, while outlining challenges in active-site identification, stability under industrial conditions, and electrolyzer integration. This review provides mechanistic insights and design guidelines for developing efficient Cu-based single-atom catalysts and practical CO2 electrolysis systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13643390/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Polarization -tilting-induced near-zero thermal expansion in PbTiO₃ nanosheets. 极化倾斜诱导PbTiO3纳米片的近零热膨胀。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc05217g

Peixi Zhang, Qiang Li, Haoyu Wang, Xiaoming Shi, Zhiguo Li, Shiqing Deng, Longlong Fan, Huaican Chen, Wen Yin, Xianran Xing

{"title":"Polarization -tilting-induced near-zero thermal expansion in PbTiO3 nanosheets.","authors":"Peixi Zhang, Qiang Li, Haoyu Wang, Xiaoming Shi, Zhiguo Li, Shiqing Deng, Longlong Fan, Huaican Chen, Wen Yin, Xianran Xing","doi":"10.1039/d6sc05217g","DOIUrl":"10.1039/d6sc05217g","url":null,"abstract":"Ferroelectrics exhibiting volumetric thermal stability are essential for thermal-shock-resistance device applications. However, due to the crucial contribution of spontaneous volume ferroelectrostriction (SVFS) to lattice expansion, the coexistence of strong ferroelectricity and zero thermal expansion (ZTE) is difficult. Herein, wide-range near-ZTE behavior (α V = 3.1 × 10-6 °C-1, 25-475 °C) and considerable ferroelectric structure (c/a ratio: 1.044) were both observed in 3.5 nm PbTiO3 nanosheets, resulting from the ab plane strain induced by polar-axis-reduction. The robust ferroelectricity and ab symmetry breaking were confirmed by piezoelectric force microscopy (PFM) and Raman spectroscopy. The neutron pair distribution function (nPDF) combined with Reverse Monte Carlo (RMC) simulations suggests that the polarization is characterized by a fixed magnitude and a tilting direction during heating, while the unit cell volume remains constant. It comes from the deviation of Ti atoms from the O6 center, along with the rotation and the deformation of the O6 octahedron. Phase-field simulations demonstrated thermally induced domain tilting towards the ab direction and supported polarization magnitude locking. The thermally stable polarization magnitude, electric-field-controllable polarization direction, and near-ZTE behavior in ultrathin two-dimensional materials hold great promise for ferroelectric applications that are immune to thermal failure. This work presents a feasible structure-guided strategy to develop high-performance nanoferroelectrics.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13643698/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Redox-state-dependent CO binding in MoFe nitrogenase: insights from EPR, IR, and QM/MM analysis. MoFe氮酶中氧化还原状态依赖的CO结合：来自EPR， IR和QM/MM分析的见解。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-07 DOI: 10.1039/d6sc05535d

Atanu Rana, Justin P Joyce, Zachary Mathe, Casey Van Stappen, Kushal Sengupta, Christian Lorent, Ingo Zebger, Laure Decamps, Serena DeBeer

{"title":"Redox-state-dependent CO binding in MoFe nitrogenase: insights from EPR, IR, and QM/MM analysis.","authors":"Atanu Rana, Justin P Joyce, Zachary Mathe, Casey Van Stappen, Kushal Sengupta, Christian Lorent, Ingo Zebger, Laure Decamps, Serena DeBeer","doi":"10.1039/d6sc05535d","DOIUrl":"10.1039/d6sc05535d","url":null,"abstract":"Nitrogenase drives biological nitrogen fixation through an eight-step cycle, in which \"n\" electrons and protons are accumulated across the E n catalytic states. Carbon monoxide (CO), a noncompetitive inhibitor for Mo nitrogenase but a substrate for V- or Fe-only nitrogenases, has been widely used as a spectroscopic probe of nitrogenase's active site. Infrared (IR) spectroscopy reports on CO binding mode and coordination environments, while electron paramagnetic resonance (EPR) spectroscopy characterizes CO-bound states via their non-integer spin states. Crystal structures reveal a µ2-bridging mode formed by substitution of a \"belt\" sulfide, suggesting that sulfide lability may be mechanistically relevant. However, the redox state at which CO binds and the assignment of the resulting non-integer spin states remain unresolved, obscuring their relationship to the N2 reduction cycle. Likewise, the mechanism and relevance of sulfide substitution remain unclear. Here, we combine static and stopped-flow IR, EPR spectroscopy, photolysis, and quantum mechanical/molecular mechanical (QM/MM) calculations, supported by non-negative matrix factorization (NMF), to investigate CO binding under varying electron flux, varying CO pressure, and H2 pressure. We find that CO binds predominantly at the E1 state, whereas EPR-active species correspond to CO-bound E2 states. H2S is identified as the preferred leaving group, and the absence of hydrides supports a stable CO-bound state that is disconnected from the reductive steps of nitrogen fixation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13670219/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149215033","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bayesian optimization- and high-throughput-guided synthesis of monofluoroalkenes via defluorinative C-C bond formation. 贝叶斯优化和高通量引导下通过脱氟C-C键形成的单氟烯烃合成。

IF 8.1 1区化学

Chemical Science Pub Date : 2026-10-06 DOI: 10.1039/d6sc05561c

Ge Gao, Qianghua Lin, Zhuoya Ma, Kuntai He, Yaxian Kong, Chenxi Yang, Chonghuan Zhang, Kuangbiao Liao

{"title":"Bayesian optimization- and high-throughput-guided synthesis of monofluoroalkenes via defluorinative C-C bond formation.","authors":"Ge Gao, Qianghua Lin, Zhuoya Ma, Kuntai He, Yaxian Kong, Chenxi Yang, Chonghuan Zhang, Kuangbiao Liao","doi":"10.1039/d6sc05561c","DOIUrl":"10.1039/d6sc05561c","url":null,"abstract":"Monofluoroalkenes are privileged fluorinated motifs in medicinal chemistry, but their selective synthesis through C-F bond activation remains challenging because of the high strength of C-F bonds and the condition-sensitive nature of defluorinative transformations. To address this challenge, this work establishes a Pd-catalyzed defluorinative C-C bond-forming strategy that couples trifluoroethyl ketones, esters, and amides with diverse organoboron reagents to deliver structurally diverse monofluoroalkenes. The integration of Bayesian optimization with high-throughput experimentation (HTE) enabled rapid condition optimization, identifying productive reaction conditions for the model substrate pair from a 376-condition table with a 53-condition Bayesian-optimization selection budget. To efficiently explore substrate generality under limited experimental budgets, the organoboron reagent space was further stratified on the basis of literature precedent, commercial availability, and structural diversity. Under the optimized condition, 970 curated substrate-reagent reaction entries were evaluated across 11 HTE plates, enabling rapid assessment of substrate compatibility and identification of productive monofluoroalkene-forming reactions. Leveraging the resulting single-condition HTE dataset, a two-stage decision-support model was further developed for reactivity classification and yield prediction, with the XGBoost model achieving an F1-score of 0.932 for classification and an R 2 of 0.852 with a mean absolute error of 4.03% for yield regression on the held-out test set. Overall, this study establishes an experimentally grounded workflow that combines Bayesian optimization, HTE, substrate-space stratification, and data-assisted modeling to accelerate reaction discovery in a condition-sensitive C-F bond activation system.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":8.1,"publicationDate":"2026-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13641191/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149104812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0