Chemical Science最新文献

筛选
英文 中文
Aromatic Cation-π Induced Multifluorescence Tunable Two-Dimensional Co-Assemblies for Encoded Information Security 芳香族阳离子-π诱导多荧光可调谐二维共组装用于编码信息安全
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-11 DOI: 10.1039/d5sc00007f
Zhao Gao, Jianxiang Sun, Lulu Shi, Wei Yuan, Wei Tian
{"title":"Aromatic Cation-π Induced Multifluorescence Tunable Two-Dimensional Co-Assemblies for Encoded Information Security","authors":"Zhao Gao, Jianxiang Sun, Lulu Shi, Wei Yuan, Wei Tian","doi":"10.1039/d5sc00007f","DOIUrl":"https://doi.org/10.1039/d5sc00007f","url":null,"abstract":"The field of light-emitting two-dimensional co-assemblies (2DCAs) is extending rapidly. Nevertheless, multifluorescence tunable 2DCAs are relatively underdeveloped, because the exploration of novel assembly strategies and noncovalent interactions to realize desirable photophysical features is still elusive. Herein, we present the first implementation of an aromatic cation-π interaction induced emissive charge transfer strategy for multifluorescence tunable 2DCAs, which are derived from fluorophore anthracene-based monomer and planar aromatic cations (pyrylium and tropylium). Benefiting from the aromatic cation-π interactions between anthracene and cationic guests, the well-regulated 2DCAs are thus successfully obtained. The resultant 2DCAs exhibit a broadened fluorescence tunable range between blue-green and red emission colors, which is simply realized by varying solvent ratio to turn on/off the aromatic cation-π emission charge transfer in the assembly/disassembly state of 2DCAs. On this basis, the programmable numbers, letters, patterns, and 3D codes with co-assembly encoded information security functions are successfully fabricated on papers, which would have a positive impact on developing supramolecular encryption materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819202","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
Accurate Prediction of the Kinetic Sequence of Physicochemical States Using Generative Artificial Intelligence 利用生成式人工智能精确预测物理化学状态的动力学序列
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc00108k
Palash Bera, Jagannath Mondal
{"title":"Accurate Prediction of the Kinetic Sequence of Physicochemical States Using Generative Artificial Intelligence","authors":"Palash Bera, Jagannath Mondal","doi":"10.1039/d5sc00108k","DOIUrl":"https://doi.org/10.1039/d5sc00108k","url":null,"abstract":"Capturing the time evolution and predicting kinetic sequences of states of physicochemical systems present significant challenges due to the precision and computational effort required. In this study, we demonstrate that ` Generative Pre-trained Transformer (GPT)', an artificial intelligence model renowned for machine translation and natural language processing, can be effectively adapted to predict the dynamical state-to-state transition kinetics of biologically relevant physicochemical systems. Specifically, by using sequences of time-discretized states from Molecular Dynamics (MD) simulation trajectories akin to vocabulary corpus of a language, we show that a GPT-based model can learn the complex syntactic and semantic relationships within the trajectory. This enables GPT to predict kinetically accurate sequences of states for a diverse set of biomolecules of varying complexity, at a much quicker pace than traditional MD simulations and with a better efficiency than other base-line time-series prediction approaches. More significantly, the approach is found to be equally adept at forecasting the time evolution of out-of-equilibrium active systems that do not maintain detailed balance. An analysis of the mechanism inherent in GPT reveals crucial role of `self-attention mechanism' in capturing the long-range correlations necessary for accurate state-to-state transition predictions. Together, our results highlight the generative artificial intelligence’s ability to generate kinetic sequence of states of physicochemical systems with statistical precision.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819253","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
A Unified Approach to Meta-Selective Methylation, Mono-, Di- and Trifluoromethylation of Arenes 芳烃的元选择性甲基化、单、二和三氟甲基化的统一方法
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc01367d
Elisa Y. Lai, Lutz Ackermann, Magnus J. Johansson
{"title":"A Unified Approach to Meta-Selective Methylation, Mono-, Di- and Trifluoromethylation of Arenes","authors":"Elisa Y. Lai, Lutz Ackermann, Magnus J. Johansson","doi":"10.1039/d5sc01367d","DOIUrl":"https://doi.org/10.1039/d5sc01367d","url":null,"abstract":"Matched molecular series (MMS) are series of molecules that differ only by a single modification at a specific site. The synthesis of MMS is a desirable strategy in drug discovery campaigns. Small aliphatic motifs, notably methyl, mono-, di- and trifluoromethyl substituents (C<small><sub>1</sub></small> units), are known to have profound effects on the physiochemical properties and/or potency of drug candidates. In this context, we herein report a unique strategy for achieving direct <em>meta</em>-selective methylation, mono-, di-, and trifluoromethylation from the same parent compound. This approach takes advantage of a highly <em>meta</em>-selective ruthenium(II)-catalyzed alkylation, followed by a subsequent photocatalyzed protodecarboxylation or silver-mediated fluorodecarboxylation to reveal the (fluoro)methyl moiety. This method enables the late-stage diversification access to MMS in small molecules bearing a variety of orienting groups as well as bio-relevant molecules containing complex functionalities, bypassing the need for <em>de novo</em> synthesis to access individual compounds in a series. Moreover, key physiochemical properties of drug candidates were successfully modulated, highlighting opportunities to accelerate medicinal chemistry programs in a sustainable fashion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819776","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
Accelerated Click Reactions using Boronic Acids for Heterocyclic Synthesis in Microdroplets 利用硼酸在微滴中进行杂环合成的加速点击反应
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc00851d
Jyotirmoy Ghosh, R. Graham Cooks
{"title":"Accelerated Click Reactions using Boronic Acids for Heterocyclic Synthesis in Microdroplets","authors":"Jyotirmoy Ghosh, R. Graham Cooks","doi":"10.1039/d5sc00851d","DOIUrl":"https://doi.org/10.1039/d5sc00851d","url":null,"abstract":"Click chemistry is important for its simplicity and versatility, however, condensation-based click reactions are limited by the general requirement of high temperatures and catalysts. Here, we report accelerated click reactions using boronic acids in microdroplets under ambient conditions without catalyst. The reaction between 2-formyl phenylboronic acid (2-FPBA) and substituted amines leads to the formation of multi-step click products, including iminoboronates, boroxines, thiazolidines, and diazaborines, depending on the selected amine. The reactions occur during microdroplet flight and are three orders of magnitude faster than the corresponding bulk reactions. MS and NMR spectral analysis confirmed the nature of the products. We suggest that the air-liquid interface of microdroplets serves both as a superacid and as a drying surface, facilitating dehydration by its superacidicity to access these products. We also demonstrate the application of these accelerated reactions as a late-stage functionalization (LSF) tool to access a range of antihistamine drug derivatives.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813820","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
Boosting near-infrared-triggered photon upconversion in optical nanomaterials via lanthanide-doped nanoparticle sensitization† 通过镧系掺杂纳米颗粒增敏增强光学纳米材料中近红外触发的光子上转换
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc00937e
Jiangshan Luo, Jun-Jian Shen, Xingwen Cheng, Yan Liu, Xiulian Yin, Tianxi Hu, Guangxin Fan, Jianming Zhang, Wei Zheng, Xueyuan Chen
{"title":"Boosting near-infrared-triggered photon upconversion in optical nanomaterials via lanthanide-doped nanoparticle sensitization†","authors":"Jiangshan Luo, Jun-Jian Shen, Xingwen Cheng, Yan Liu, Xiulian Yin, Tianxi Hu, Guangxin Fan, Jianming Zhang, Wei Zheng, Xueyuan Chen","doi":"10.1039/d5sc00937e","DOIUrl":"https://doi.org/10.1039/d5sc00937e","url":null,"abstract":"A broad spectrum of optical nanomaterials, including organic molecules, quantum dots, and metallic nanoparticles, have attracted great attention in fields such as biological imaging, data storage, solid-state lasers and solar energy conversion owing to their nonlinear optical properties facilitated by the two-photon absorption process. However, their nonlinear optical properties, particularly photon upconversion triggered by near-infrared light, are constrained by a limited multiphoton absorption cross-section, requiring costly pulsed laser with high-density excitation. Herein, we present a straightforward and versatile strategy to enhance upconversion luminescence in various optical nanomaterials via sensitization with lanthanide-doped nanoparticles. This approach not only broadens the near-infrared responsivity of these luminescent nanomaterials but also introduces novel emission profiles to the lanthanide-doped nanoparticles, enabling multidimensional tunability in terms of wavelength, lifetime, and polarization under low-density excitation. Concentration-dependent photoluminescence spectra and decay curves reveal a radiative energy transfer upconversion mechanism. These findings provide a general strategy for controlling photon upconversion in a wide range of luminescent nanomaterials, paving the way for innovative and versatile applications in diverse fields.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813831","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
Cooperative promotion of electroreduction of CO to n-propanol by *CO enrichment and proton regulation *CO富集与质子调控协同促进CO电还原制正丙醇
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc00274e
Rongxing Qiu, Linxiao Cui, Li Peng, Olga Syzgantseva, Jiaran Li, Nan Fang, Maria Syzgantseva, Yuan Jiang, Jie Zhang, Bingxing Zhang, Ling-Zhi Ding, Yangyang Dong, Tianwei Xue, Cheng Li, Jin-Chao Dong, Jin-Yu Ye, Isil Akpinar, Shuliang Yang, Jun Li, Jianling Zhang, Jian-Feng Li, Buxing Han
{"title":"Cooperative promotion of electroreduction of CO to n-propanol by *CO enrichment and proton regulation","authors":"Rongxing Qiu, Linxiao Cui, Li Peng, Olga Syzgantseva, Jiaran Li, Nan Fang, Maria Syzgantseva, Yuan Jiang, Jie Zhang, Bingxing Zhang, Ling-Zhi Ding, Yangyang Dong, Tianwei Xue, Cheng Li, Jin-Chao Dong, Jin-Yu Ye, Isil Akpinar, Shuliang Yang, Jun Li, Jianling Zhang, Jian-Feng Li, Buxing Han","doi":"10.1039/d5sc00274e","DOIUrl":"https://doi.org/10.1039/d5sc00274e","url":null,"abstract":"The CO2/CO electroreduction reaction (CO2RR/CORR) to liquid products presents an enticing pathway to store intermittent renewable electricity. However, the selectivity for desirable high-value C3 products, such as n-propanol, remains unsatisfactory in CO2RR/CORR. Here, we report that *CO enrichment and proton regulation cooperatively enhance C1-C2 coupling by increasing CO pressure and utilizing proton sponge modification, promoting the production of n-propanol over a Cu0/Cu⁺ nanosheet catalyst in the CORR. We obtain an impressive Faradaic efficiency (FE) of 44.0% ± 2.3% for n-propanol at a low potential of −0.44 V vs. reversible hydrogen electrode (RHE) under 3 bar CO. Experimental results demonstrated that *H intermediates could be regulated by proton sponge modification. In situ characterizations combined with density functional theory (DFT) calculations validate that Cu+ species exist stably in proton sponge-modified Cu-based catalysts along with appropriate *CO coverage. This design facilitates the potential-determining C1-C1 and C1-C2 coupling steps and contributes to the n-propanol production.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"217 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813819","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
The Impact of Whole-Molecule Disorder on Spin-Crossover in a Family of Isomorphous Molecular Crystals 一类同形分子晶体中全分子无序对自旋交叉的影响
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc00090d
Holly E. Sephton, Rhiannon L. Watson, Namrah Shahid, Hari Babu Vasili, Daniel Baker, Dipankar Saha, Izar Capel Berdiell, Christopher M. Pask, Oscar Cespedes, Malcolm Halcrow
{"title":"The Impact of Whole-Molecule Disorder on Spin-Crossover in a Family of Isomorphous Molecular Crystals","authors":"Holly E. Sephton, Rhiannon L. Watson, Namrah Shahid, Hari Babu Vasili, Daniel Baker, Dipankar Saha, Izar Capel Berdiell, Christopher M. Pask, Oscar Cespedes, Malcolm Halcrow","doi":"10.1039/d5sc00090d","DOIUrl":"https://doi.org/10.1039/d5sc00090d","url":null,"abstract":"Treatment of 2-(pyrazol-1-yl)-6-fluoropyridine with one equiv of the appropriate 4-substituted 1<em>H</em>-pyrazole in the presence of sodium hydride gives moderate yields of 2-(pyrazol-1-yl)-6-(4-methylpyrazol-1-yl)pyridine (L<small><sup>Me</sup></small>), 2-(pyrazol-1-yl)-6-(4-fluoropyrazol-1-yl)pyridine (L<small><sup>F</sup></small>), 2-(pyrazol-1-yl)-6-(4-chloropyrazol-1-yl)pyridine (L<small><sup>Cl</sup></small>) and 2-(pyrazol-1-yl)-6-(4-bromopyrazol-1-yl)pyridine (L<small><sup>Br</sup></small>). Single crystals of [Fe(L<small><sup>R</sup></small>)<small><sub>2</sub></small>]Z<small><sub>2</sub></small> (R = Me, F or Br; Z<small><sup>−</sup></small> = BF<small><sub>4</sub></small><small><sup>−</sup></small> or ClO<small><sub>4</sub></small><small><sup>−</sup></small>) are often well-formed, but are poor diffractors of X-rays. An analysis of [Fe(L<small><sup>Me</sup></small>)<small><sub>2</sub></small>][ClO<small><sub>4</sub></small>]<small><sub>2</sub></small> showed non-statistical positional disorder of the methyl substituents, leading to whole molecule disorder in each residue of the asymmetric unit. Single crystals of [Fe(L<small><sup>Br</sup></small>)<small><sub>2</sub></small>][BF<small><sub>4</sub></small>]<small><sub>2</sub></small> are isomorphous with the L<small><sup>Me</sup></small> complex, and but less substituent disorder. All the complex salts are isomorphous by powder diffraction, and show thermal spin-transitions whose cooperativity differs from gradual (R = Me) to abrupt and hysteretic (R = Br). Some of the cooperative transitions exhibit irregular, closely spaced discontinuities which do not appear to be caused by crystallographic phase changes, and may reflect local heterogeneities caused by the cation disorder. No aspect of their crystal packing appears to correlate with their spin-transition cooperativity. However, weaker cooperativity may correlate with increased cation disorder in this system, which merits further investigation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"97 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813583","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
Tuning Covalent Bonding in Znic-Based Hybrid Halides towards Tunable Room-Temperature Phosphorescence 调谐 Znic 基杂化卤化物中的共价键,实现可调谐室温磷光
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc00931f
Yibo Cui, Jiawei Lin, Kunjie Liu, Yuhe Shao, Dong Zhao, Zhongnan Guo, Jing Zhao, Zhiguo Xia, Quanlin Liu
{"title":"Tuning Covalent Bonding in Znic-Based Hybrid Halides towards Tunable Room-Temperature Phosphorescence","authors":"Yibo Cui, Jiawei Lin, Kunjie Liu, Yuhe Shao, Dong Zhao, Zhongnan Guo, Jing Zhao, Zhiguo Xia, Quanlin Liu","doi":"10.1039/d5sc00931f","DOIUrl":"https://doi.org/10.1039/d5sc00931f","url":null,"abstract":"Organic-inorganic metal halides with tunable and state room-temperature phosphorescence (RTP) properties receive broad interests in advanced luminescent materials. Herein, 2-(methylamino)pyridine (MAP), 2-[(methylamino)methyl]pyridine (MAMP), and 2-(2-methylaminoethyl)pyridine (MAEP) were designed and hybridized with Zn2+ and Cl-/Br-, yielding 11 hybrid materials. MAP-based compounds, with a narrow bandgap (3.57 eV), exhibit limited RTP due to inefficient intersystem crossing (ISC) and unstable triplet excitons. In contrast, MAMP (4.49 eV) and MAEP (4.50 eV)-based compounds achieve enhanced RTP through bandgap alignment with Zn halides, enabling efficient energy transfer, ISC, and triplet exciton stabilization via strong hydrogen bonding and π-conjugation effects. Covalent bonding in MAMP and MAEP compounds provides greater rigidity and exciton stability than hydrogen-bonded systems, resulting in prolonged afterglow durations. While Br- bonding enhances ISC and spin-orbit coupling (SOC), and the weak interactions increase non-radiative decay, further reducing afterglow duration. Density functional theory calculations confirm the enhanced SOC in MAMP and MAEP compounds, further improving RTP efficiency. This work demonstrates the precise control of RTP properties, highlighting the potential in advanced anti-counterfeiting and emerging photonics applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"35 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813825","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
Unraveling the Mechanisms of Ketene Generation and Transformation in Syngas-to-Olefins Conversion over ZnCrOx|SAPO-34 Catalysts ZnCrOx|SAPO-34催化剂催化合成气制烯烃过程中烯酮生成和转化机理的研究
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc01651g
Zhuo-Yan Yao, Sicong Ma, Zhipan Liu
{"title":"Unraveling the Mechanisms of Ketene Generation and Transformation in Syngas-to-Olefins Conversion over ZnCrOx|SAPO-34 Catalysts","authors":"Zhuo-Yan Yao, Sicong Ma, Zhipan Liu","doi":"10.1039/d5sc01651g","DOIUrl":"https://doi.org/10.1039/d5sc01651g","url":null,"abstract":"Ketene was identified as an intermediate in syngas-to-olefins (STO) conversion catalyzed by metal oxide-zeolite composites, which sparked the hot debate on its formation mechanism and catalytic roles. Here we employed large-scale atomic simulations using global neural network potentials to explore the STO reaction pathways, and microkinetic simulations to couple the reaction kinetics in ZnCrO<small><sub>x</sub></small>|SAPO-34 composite sites. Our results demonstrate that a majority of ketene (86.1%) originates from the methanol carbonylation-to-ketene route (CH<small><sub>3</sub></small>OH* + H* -&gt; CH<small><sub>3</sub></small>* + H<small><sub>2</sub></small>O -&gt; CH<small><sub>3</sub></small>* + CO* -&gt; CH<small><sub>2</sub></small>CO* + H*) nearby zeolite acidic sites, where methanol is produced through conventional syngas-to-methanol on Zn<small><sub>3</sub></small>Cr<small><sub>3</sub></small>O<small><sub>8 </sub></small>(0001) surface, while the minority of ketene (13.9%) arises from a direct CHO*-CO* coupling (CHO* + CO* + H* -&gt; CHOCO* + H* -&gt; CH<small><sub>2</sub></small>CO + O*) on Zn<small><sub>3</sub></small>Cr<small><sub>3</sub></small>O<small><sub>8</sub></small>. The presence of the ketene pathway significantly alters the catalytic performance in zeolite, as methanol carbonylation to ketene is kinetically more efficient in competing with conventional methanol-to-olefins (MTO) and thus predominantly drives the product to ethene. Based on our microkinetic simulation, it is the methanol carbonylation activity in zeolite that dictates the performance of STO catalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"75 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813830","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
Visible-light-mediated site-selective C(sp2)–H alkylation of tropones facilitates semi-synthesis of cephafortunoids A and B 可见光介导的位点选择性C(sp2) -H烷基化有利于类头孢甲酮A和B的半合成
IF 8.4 1区 化学
Chemical Science Pub Date : 2025-04-10 DOI: 10.1039/d5sc01006c
Qi-Xiang Zeng, Cheng-Yu Zheng, Zhan-Peng Ge, Jin-Xin Zhao, Jian-Min Yue
{"title":"Visible-light-mediated site-selective C(sp2)–H alkylation of tropones facilitates semi-synthesis of cephafortunoids A and B","authors":"Qi-Xiang Zeng, Cheng-Yu Zheng, Zhan-Peng Ge, Jin-Xin Zhao, Jian-Min Yue","doi":"10.1039/d5sc01006c","DOIUrl":"https://doi.org/10.1039/d5sc01006c","url":null,"abstract":"The synthesis of functionalized tropones constitutes an underexplored chemical space, primarily due to the intrinsic structural properties of the aromatic nucleus. This predicament has impeded extensive investigation into their potential applications in organic and medicinal chemistry. Here, we report a mild and straightforward visible-light-mediated protocol for the α-site-selective C(sp<small><sup>2</sup></small>)–H alkylation of tropones, employing unactivated secondary amines as alkylating agents. This method yields up to 89% in 48 examples, and is significantly amenable to late-stage functionalization. The utility is showcased by the effective chemical transformation of fortunolide A to cephafortunoids A and B, representing the first synthetic entry to this unique class of C<small><sub>20</sub></small><em>Cephalotaxus</em> troponoids. Significantly, this achievement reinforces the chemical feasibility of the newly hypothesized biosynthesis involving direct methylation via radical <em>S</em>-adenosylmethionine (SAM)-dependent methyltransferases.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813826","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
0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
相关产品
×
本文献相关产品
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信