首页 > 最新文献

Advanced Synthesis & Catalysis最新文献

英文 中文
Machine Learning Guided d-Orbital Electron Modulated Graphene-Based Catalysts for Enhanced Electrochemical Ammonia Synthesis 机器学习引导的d轨道电子调制石墨烯基催化剂增强电化学氨合成
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-05 DOI: 10.1002/adsc.70343
Gengwei Wu, Yusen Du, Yan Zhuang, Ying Wang, Yujing Lv, Rui Chen, Zhengxin Ding, Rusheng Yuan, Zizhong Zhang, Jinlin Long

The selective reduction of atmospheric nitrogen to ammonia under ambient conditions via electrochemical methods has emerged as a promising alternative to the Haber–Bosch process. Despite its feasibility, the performance of core catalysts has been constrained by the strength of the π-backdonation between the d-orbital electrons of the metal active center and the antibonding orbitals of nitrogen. In this study, we propose constructing M-N3 structures and introducing auxiliary metals to cooperatively regulate the local crystal field to enhance the π-backdonation and promote nitrogen activation. By employing machine learning (ML) to analyze the electronic structure and using the number of d electrons and electronegativity of the metal as key descriptors, we successfully established a quantitative relationship between the π-backdonation strength, catalytic activity and identified tungsten and molybdenum as high-performance candidate metals. The corresponding graphene-based catalysts were successfully prepared experimentally, with the tungsten-based catalyst achieving an ammonia production rate of 150.08 μg h−1 mgcat−1 and a Faraday efficiency of 85.7% at −0.9 V vs. RHE. Density functional theory (DFT) calculations jointly confirmed that the strategy of regulating the local crystal field effectively optimized the d-orbital energy level splitting and electron occupation, promoting the formation of the π-backdonation. This work demonstrates the effectiveness of the crystal field engineering strategy in modulating d-orbital electrons through machine learning and DFT calculations and confirms the unique guiding role of machine learning in the reverse design of high-performance electrocatalysts.

在环境条件下,通过电化学方法将大气氮选择性还原为氨已成为Haber-Bosch工艺的一种有前途的替代方法。尽管可行,但核心催化剂的性能受到金属活性中心的d轨道电子与氮的反键轨道之间的π反给给强度的制约。在本研究中,我们提出构建M-N3结构并引入辅助金属协同调节局部晶体场,以增强π-反给能,促进氮活化。利用机器学习(ML)技术分析金属的电子结构,并以金属的d电子数和电负性为关键描述符,成功建立了π反给予强度与催化活性之间的定量关系,并确定了钨和钼为高性能候选金属。实验成功制备了相应的石墨烯基催化剂,其中钨基催化剂在−0.9 V相对于RHE下的产氨率为150.08 μg h−1 mgcat−1,法拉第效率为85.7%。密度泛函理论(DFT)计算共同证实了调节局部晶体场的策略有效地优化了d轨道能级分裂和电子占据,促进了π-反给能的形成。这项工作证明了晶体场工程策略在通过机器学习和DFT计算调制d轨道电子方面的有效性,并证实了机器学习在高性能电催化剂的逆向设计中的独特指导作用。
{"title":"Machine Learning Guided d-Orbital Electron Modulated Graphene-Based Catalysts for Enhanced Electrochemical Ammonia Synthesis","authors":"Gengwei Wu,&nbsp;Yusen Du,&nbsp;Yan Zhuang,&nbsp;Ying Wang,&nbsp;Yujing Lv,&nbsp;Rui Chen,&nbsp;Zhengxin Ding,&nbsp;Rusheng Yuan,&nbsp;Zizhong Zhang,&nbsp;Jinlin Long","doi":"10.1002/adsc.70343","DOIUrl":"10.1002/adsc.70343","url":null,"abstract":"<p>The selective reduction of atmospheric nitrogen to ammonia under ambient conditions via electrochemical methods has emerged as a promising alternative to the Haber–Bosch process. Despite its feasibility, the performance of core catalysts has been constrained by the strength of the π-backdonation between the d-orbital electrons of the metal active center and the antibonding orbitals of nitrogen. In this study, we propose constructing M-N<sub>3</sub> structures and introducing auxiliary metals to cooperatively regulate the local crystal field to enhance the π-backdonation and promote nitrogen activation. By employing machine learning (ML) to analyze the electronic structure and using the number of d electrons and electronegativity of the metal as key descriptors, we successfully established a quantitative relationship between the π-backdonation strength, catalytic activity and identified tungsten and molybdenum as high-performance candidate metals. The corresponding graphene-based catalysts were successfully prepared experimentally, with the tungsten-based catalyst achieving an ammonia production rate of 150.08 μg h<sup>−1</sup> mg<sub>cat</sub><sup>−1</sup> and a Faraday efficiency of 85.7% at −0.9 V vs. RHE. Density functional theory (DFT) calculations jointly confirmed that the strategy of regulating the local crystal field effectively optimized the d-orbital energy level splitting and electron occupation, promoting the formation of the π-backdonation. This work demonstrates the effectiveness of the crystal field engineering strategy in modulating d-orbital electrons through machine learning and DFT calculations and confirms the unique guiding role of machine learning in the reverse design of high-performance electrocatalysts.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 6","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147360089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Recent Developments in Transition-Metal-Catalyzed Tandem CH Activation/Cyclization of α,ω-Diynes 过渡金属催化串联C?H α,ω-Diynes的活化/环化
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-04 DOI: 10.1002/adsc.70339
Fen Xu, Jia-Qi Huo, Ya-Peng Li, Fan-Wang Zeng, Shi-Yu Zhang, Yuan Feng, Luciano Barboni

Transition-metal-catalyzed CH activation has emerged as a powerful tool for constructing diverse heterocycles and efficiently increasing molecular complexity in a single operation. Compared with the well-studied diyne [2 + 2 + 2] cycloaddition, diyne-involved CH functionalization represents a promising evolution of this field. The inherent reactivity of diynes enables sequential participation of both alkyne units in relay processes, a feature central to their utility. Recent years have witnessed remarkable progress in diyne-based CH functionalization/cyclization with exquisite site- and chemoselectivity, spanning substrate control strategies, catalysis design, reaction development, mechanistic insights, substrate scope, and practical applications. Organized by the type of diyne and reaction patterns, this review highlights recent advances in transition-metal-catalyzed tandem CH functionalization/cyclization reactions of 1,6-diynes, 1,5-diynes, 1,4-diynes, and other tethered diyne substrates, with a focus on the assembly of 1,3-dienes, polycyclic aromatic hydrocarbons, π-conjugated polymers, polyheterocycles, and related structures. Notably, this review focuses exclusively on reactions where both alkyne units participate in tandem processes, excluding cases where only one alkyne acts as a π-coupling reagent.

过渡金属催化的C - H活化已成为构建多种杂环和在单一操作中有效增加分子复杂性的强大工具。与已被广泛研究的双炔[2 + 2 + 2]环加成相比,双炔参与的C - H功能化代表了该领域的一个有前途的发展方向。炔的固有反应性使两个炔单元在接力过程中顺序参与,这是其效用的核心特征。近年来,在基于二炔的C - H功能化/环化方面取得了显著进展,具有良好的位点和化学选择性,涵盖底物控制策略,催化设计,反应开发,机理见解,底物范围和实际应用。根据二炔的类型和反应模式,本文综述了过渡金属催化1,6-二炔、1,5-二炔、1,4-二炔和其他系结二炔底物的串联C -羟基功能化/环化反应的最新进展,重点介绍了1,3-二烯、多环芳烃、π共轭聚合物、多杂环和相关结构的组装。值得注意的是,本综述只关注两个炔单元参与串联过程的反应,不包括只有一个炔作为π偶联试剂的情况。
{"title":"Recent Developments in Transition-Metal-Catalyzed Tandem CH Activation/Cyclization of α,ω-Diynes","authors":"Fen Xu,&nbsp;Jia-Qi Huo,&nbsp;Ya-Peng Li,&nbsp;Fan-Wang Zeng,&nbsp;Shi-Yu Zhang,&nbsp;Yuan Feng,&nbsp;Luciano Barboni","doi":"10.1002/adsc.70339","DOIUrl":"10.1002/adsc.70339","url":null,"abstract":"<p>Transition-metal-catalyzed C<span></span>H activation has emerged as a powerful tool for constructing diverse heterocycles and efficiently increasing molecular complexity in a single operation. Compared with the well-studied diyne [2 + 2 + 2] cycloaddition, diyne-involved C<span></span>H functionalization represents a promising evolution of this field. The inherent reactivity of diynes enables sequential participation of both alkyne units in relay processes, a feature central to their utility. Recent years have witnessed remarkable progress in diyne-based C<span></span>H functionalization/cyclization with exquisite <i>site</i>- and chemoselectivity, spanning substrate control strategies, catalysis design, reaction development, mechanistic insights, substrate scope, and practical applications. Organized by the type of diyne and reaction patterns, this review highlights recent advances in transition-metal-catalyzed tandem C<span></span>H functionalization/cyclization reactions of 1,6-diynes, 1,5-diynes, 1,4-diynes, and other tethered diyne substrates, with a focus on the assembly of 1,3-dienes, polycyclic aromatic hydrocarbons, <i>π</i>-conjugated polymers, polyheterocycles, and related structures. Notably, this review focuses exclusively on reactions where both alkyne units participate in tandem processes, excluding cases where only one alkyne acts as a <i>π</i>-coupling reagent.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 6","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147360088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Recent Progress in Asymmetric Oxidative Radical–Polar Crossover Reactions 不对称氧化自由基-极性交叉反应研究进展
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-04 DOI: 10.1002/adsc.70315
Xiaochong Guo, Kangping Wu, Mianling Zhang

Radical–polar crossover (RPCO) has emerged as a powerful synthetic strategy, using the complementary properties of both radical and classical polar chemistry. Radical–polar crossover, especially its oxidative radical–polar crossover (ORPCO), facilitates efficient asymmetric synthesis by converting radical intermediates to carbocations, which allow the formation of enantioselective bonds. This ability to form CC, CO, and CN bonds underlines its significant potential for late–stage functionalization of complex molecules and for diversification of medicinal products. This review summarizes the recent developments in the asymmetric ORPCO domain, including catalytic strategies, transformation mechanisms, and current characteristics. Research into new catalytic strategies and asymmetric bonding paradigms is an important frontier of future research, with the potential to significantly increase the scale and usefulness of ORPCO reactions.

自由基-极性交叉(RPCO)作为一种强大的合成策略,利用了自由基化学和经典极性化学的互补性质。自由基-极性交叉,特别是氧化自由基-极性交叉(ORPCO),通过将自由基中间体转化为碳正离子,促进了高效的不对称合成,从而形成对映选择性键。这种形成C - C、C - O和C - N键的能力强调了其在复杂分子的后期功能化和医药产品多样化方面的巨大潜力。本文综述了近年来不对称ORPCO结构域的研究进展,包括催化策略、转化机制和当前特征。研究新的催化策略和不对称键模式是未来研究的重要前沿,有可能显著提高ORPCO反应的规模和用途。
{"title":"Recent Progress in Asymmetric Oxidative Radical–Polar Crossover Reactions","authors":"Xiaochong Guo,&nbsp;Kangping Wu,&nbsp;Mianling Zhang","doi":"10.1002/adsc.70315","DOIUrl":"10.1002/adsc.70315","url":null,"abstract":"<p>Radical–polar crossover (RPCO) has emerged as a powerful synthetic strategy, using the complementary properties of both radical and classical polar chemistry. Radical–polar crossover, especially its oxidative radical–polar crossover (ORPCO), facilitates efficient asymmetric synthesis by converting radical intermediates to carbocations, which allow the formation of enantioselective bonds. This ability to form C<span></span>C, C<span></span>O, and C<span></span>N bonds underlines its significant potential for late–stage functionalization of complex molecules and for diversification of medicinal products. This review summarizes the recent developments in the asymmetric ORPCO domain, including catalytic strategies, transformation mechanisms, and current characteristics. Research into new catalytic strategies and asymmetric bonding paradigms is an important frontier of future research, with the potential to significantly increase the scale and usefulness of ORPCO reactions.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 6","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147360098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Mechanochemical Synthesis of N, N-Disubstituted 2-Amino-Thiazolines, and 1,3-Thiazolidine-2-Imine Hydrochlorides 机械化学合成N, N-二取代2-氨基噻唑啉和1,3-噻唑烷-2-亚胺盐酸盐
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-04 DOI: 10.1002/adsc.70340
Kamil Hanek, Barbara Kaczmarek, Dawid Frąckowiak, Patrycja Żak

The mechanochemical synthesis of 4,5-dihydro-1,3-thiazol-2-amines and 1,3-thiazolidine-2-imine hydrochlorides has been performed starting from chloroalkyl isothiocyanate and amines in the presence of potassium carbonate. The proposed procedure is efficient under transition metal- and solvent-free ball-milling conditions with the use of a mixer mill. The reactions are selective and show no significant decrease in yields across a broad scope of substrates bearing different functional groups. Moreover, the successful 1 g scale-up experiment demonstrates the practical applicability of the method.

以异硫氰酸氯烷基酯和胺为原料,在碳酸钾存在下,机械化学合成了4,5-二氢-1,3-噻唑-2-胺和1,3-噻唑烷-2-亚胺盐酸盐。该方法在过渡金属和无溶剂球磨条件下使用混合磨是有效的。这些反应是选择性的,并且在具有不同官能团的底物范围内没有显示出产率的显著下降。此外,成功的1 g放大实验证明了该方法的实际适用性。
{"title":"Mechanochemical Synthesis of N, N-Disubstituted 2-Amino-Thiazolines, and 1,3-Thiazolidine-2-Imine Hydrochlorides","authors":"Kamil Hanek,&nbsp;Barbara Kaczmarek,&nbsp;Dawid Frąckowiak,&nbsp;Patrycja Żak","doi":"10.1002/adsc.70340","DOIUrl":"10.1002/adsc.70340","url":null,"abstract":"<p>The mechanochemical synthesis of 4,5-dihydro-1,3-thiazol-2-amines and 1,3-thiazolidine-2-imine hydrochlorides has been performed starting from chloroalkyl isothiocyanate and amines in the presence of potassium carbonate. The proposed procedure is efficient under transition metal- and solvent-free ball-milling conditions with the use of a mixer mill. The reactions are selective and show no significant decrease in yields across a broad scope of substrates bearing different functional groups. Moreover, the successful 1 g scale-up experiment demonstrates the practical applicability of the method.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 6","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147361002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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‐Driven Wolff Rearrangement/Formal (3+2) Cyclization of α‐Diazoketones with Bicyclo[1.1.0]butanes: Efficient and Highly Regioselective Access Oxabicyclo‐[2.1.1]hexane Scaffolds α -重氮酮与双环[1.1.0]丁烷的可见光驱动Wolff重排/正(3+2)环化:高效和高区域选择性地获得氧双环[2.1.1]己烷支架
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-03 Epub Date: 2025-12-23 DOI: 10.1002/adsc.70212
Li Zhang , Xiang Li , Jin Zhou , Yulin Luo , Qiwen Pang , Wei Huang , Bo Han , Xiang‐Hong He
The development of oxygen‐containing three‐dimensional bicyclic scaffolds as bioisosteres of aromatic rings is of increasing importance for improving physicochemical and pharmacokinetic profiles in modern pharmaceutical development. Herein, we report a catalyst‐ and additive‐free strategy to access a series of multifunctional oxa‐bicyclo[2.1.1]hexane derivatives in a single operation from readily accessible α‐diazoketones and bicyclo[1.1.0]butanes. The process involves a visible‐light‐mediated sequential Wolff rearrangement/[2π + 2σ] cycloaddition. Generally, this reaction proceeds under mild conditions and features broad substrate scope, good functional group tolerance, and high regiospecificity. The synthetic utility of this method is demonstrated through diverse synthetic transformations of the resulting products. Furthermore, control experiments and mechanistic studies were conducted, and a plausible mechanism is proposed to rationalize the observed efficiency.
在现代药物开发中,开发含氧三维双环支架作为芳香环的生物同位异构体对改善药物的理化和药代动力学特征具有越来越重要的意义。在此,我们报告了一种无催化剂和添加剂的策略,可以在一次操作中从容易获得的α -重氮酮和双环[1.1.0]丁烷中获得一系列多功能的氧-双环[2.1.1]己烷衍生物。该过程涉及可见光介导的顺序Wolff重排/[2 π + 2 σ]环加成。一般来说,该反应在温和的条件下进行,具有底物范围广、功能基耐受性好、区域特异性高的特点。通过对所得产物进行多种合成变换,证明了该方法的综合效用。此外,还进行了对照实验和机理研究,并提出了一种合理的机制来合理化观察到的效率。
{"title":"Visible Light‐Driven Wolff Rearrangement/Formal (3+2) Cyclization of α‐Diazoketones with Bicyclo[1.1.0]butanes: Efficient and Highly Regioselective Access Oxabicyclo‐[2.1.1]hexane Scaffolds","authors":"Li Zhang ,&nbsp;Xiang Li ,&nbsp;Jin Zhou ,&nbsp;Yulin Luo ,&nbsp;Qiwen Pang ,&nbsp;Wei Huang ,&nbsp;Bo Han ,&nbsp;Xiang‐Hong He","doi":"10.1002/adsc.70212","DOIUrl":"10.1002/adsc.70212","url":null,"abstract":"<div><div>The development of oxygen‐containing three‐dimensional bicyclic scaffolds as bioisosteres of aromatic rings is of increasing importance for improving physicochemical and pharmacokinetic profiles in modern pharmaceutical development. Herein, we report a catalyst‐ and additive‐free strategy to access a series of multifunctional oxa‐bicyclo[2.1.1]hexane derivatives in a single operation from readily accessible α‐diazoketones and bicyclo[1.1.0]butanes. The process involves a visible‐light‐mediated sequential Wolff rearrangement/[2<em>π</em> + 2<em>σ</em>] cycloaddition. Generally, this reaction proceeds under mild conditions and features broad substrate scope, good functional group tolerance, and high regiospecificity. The synthetic utility of this method is demonstrated through diverse synthetic transformations of the resulting products. Furthermore, control experiments and mechanistic studies were conducted, and a plausible mechanism is proposed to rationalize the observed efficiency.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70212"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145801133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Solvent‐Switchable Regiodivergent Chlorination of Quinone Monoacetals: A Practical Route to 2‐ and 3‐Chlorophenols 醌类单缩醛的溶剂可切换区域发散氯化反应:制备2-和3-氯酚的实用途径
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-03 Epub Date: 2026-03-07 DOI: 10.1002/adsc.70234
Pragya Sharma , Sharda Pasricha , Sunny Singh , Mainak Dey , Chinmoy Kumar Hazra
Regioselective, metal‐free, CH chlorination of phenols is challenging. These reactions generally proceed via electrophilic aromatic substitution, resulting in pure 2‐ or 4‐chlorinated products or a mixture of 2‐ and 4‐substituted isomers. However, 3‐substitution is electronically forbidden in these cases. Electrophilic aromatic chlorination involves toxic reagents, low tolerance for functional groups, and the generation of waste products from the chlorinating agent. Improvizations involving classical preformed chlorinating agents, oxidative chlorination, and transition metal catalysis, among others, require harsh conditions, high temperatures, directing groups, and low atom economy, despite achieving high selectivity. Few reports have also utilized the activation of arenes to facilitate regioselective nucleophilic chlorination. In a unique progression in phenol chemistry, we report a regioselective, indirect, catalyst‐ and metal‐free synthesis of 2‐chlorophenols via the chlorination of quinone monoacetals (QMA), derived from the oxidative dearomatization of phenol, using dimethyl chlorohydrosilane as a chloride source. Further, Brønsted acid‐catalyzed chlorination of QMA–MBH adducts afforded regioselective, metal‐free, solvent‐switchable 3‐ or 2‐chlorophenols via a one‐pot cascade reaction. C‐2‐chlorination proceeds via Michael addition of Cl ion to the intermediate phenoxonium ion, while C‐3 chlorination occurs via Cl addition to a silane‐activated quinone intermediate. This approach is well‐suited for late‐stage functionalization in pharmaceuticals, natural products, and complex molecules.
区域选择性,无金属,C - H氯化苯酚是具有挑战性的。这些反应通常通过亲电芳香取代进行,产生纯2或4氯化产物或2和4取代异构体的混合物。然而,在这些情况下,3-取代是电子禁止的。亲电芳香族氯化涉及有毒试剂,对官能团的耐受性低,以及氯化剂产生的废物。包括经典预成型氯化剂、氧化氯化和过渡金属催化等在内的改进,尽管实现了高选择性,但需要苛刻的条件、高温、导向基团和低原子经济性。很少有报道利用芳烃的活化来促进区域选择性亲核氯化反应。在苯酚化学的一个独特进展中,我们报道了一种利用二甲基氯氢硅烷作为氯源,通过苯酚氧化脱芳反应得到的醌单缩醛(QMA)的氯化合成2-氯苯酚的区域选择性,间接,无催化剂和无金属。此外,Brønsted酸催化的QMA-MBH加合物的氯化反应通过一锅级联反应获得了区域选择性、无金属、溶剂可切换的3-或2-氯苯酚。c -2氯化反应是通过在中间苯氧鎓离子上添加Cl -离子进行的,而C-3氯化反应是通过在硅烷活化的醌中间添加Cl -离子进行的。这种方法非常适合于药物、天然产物和复杂分子的后期功能化。
{"title":"Solvent‐Switchable Regiodivergent Chlorination of Quinone Monoacetals: A Practical Route to 2‐ and 3‐Chlorophenols","authors":"Pragya Sharma ,&nbsp;Sharda Pasricha ,&nbsp;Sunny Singh ,&nbsp;Mainak Dey ,&nbsp;Chinmoy Kumar Hazra","doi":"10.1002/adsc.70234","DOIUrl":"10.1002/adsc.70234","url":null,"abstract":"<div><div>Regioselective, metal‐free, CH chlorination of phenols is challenging. These reactions generally proceed via electrophilic aromatic substitution, resulting in pure 2‐ or 4‐chlorinated products or a mixture of 2‐ and 4‐substituted isomers. However, 3‐substitution is electronically forbidden in these cases. Electrophilic aromatic chlorination involves toxic reagents, low tolerance for functional groups, and the generation of waste products from the chlorinating agent. Improvizations involving classical preformed chlorinating agents, oxidative chlorination, and transition metal catalysis, among others, require harsh conditions, high temperatures, directing groups, and low atom economy, despite achieving high selectivity. Few reports have also utilized the activation of arenes to facilitate regioselective nucleophilic chlorination. In a unique progression in phenol chemistry, we report a regioselective, indirect, catalyst‐ and metal‐free synthesis of 2‐chlorophenols via the chlorination of quinone monoacetals (QMA), derived from the oxidative dearomatization of phenol, using dimethyl chlorohydrosilane as a chloride source. Further, Brønsted acid‐catalyzed chlorination of QMA–MBH adducts afforded regioselective, metal‐free, solvent‐switchable 3‐ or 2‐chlorophenols via a one‐pot cascade reaction. C‐2‐chlorination proceeds via Michael addition of Cl<sup>−</sup> ion to the intermediate phenoxonium ion, while C‐3 chlorination occurs via Cl<sup>−</sup> addition to a silane‐activated quinone intermediate. This approach is well‐suited for late‐stage functionalization in pharmaceuticals, natural products, and complex molecules.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70234"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 Driven Copper‐Catalyzed Oxidative Alkylation of Styrenes with Sulfonium Salts and Alcohol or Acids 可见光驱动铜催化苯乙烯与磺盐和醇或酸的氧化烷基化反应
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-03 Epub Date: 2026-03-07 DOI: 10.1002/adsc.70314
Long‐Jin Zhong , Shu‐Zheng Ou , Peng‐Fei Huang , Ke‐Wen Tang , Quan Zhou , Yu Liu
We developed a three‐component intermolecular alkoxysulfurization or estersulfurization of styrenes for the synthesis of emote alkoxy (ester) substituted thioether derivatives through copper/visible light catalyzed strategy. A variety of substrates were successfully converted into the desired sulfur‐containing products in moderate to good yields, demonstrating good functional group tolerance and excellent regioselectivity. Moreover, this method can be readily applied to modify bioactive molecules. A range of substrates, including perillyl alcohol, citronellol, geraniol, L‐menthol, and cholesterol, were successfully install to olefins with high selectivity.
研究了苯乙烯分子间三组分烷氧硫化或酯硫化反应,通过铜/可见光催化策略合成远端烷氧基(酯)取代硫醚衍生物。多种底物成功转化为所需的含硫产物,产率中等至较高,表现出良好的官能团耐受性和优异的区域选择性。此外,该方法可以很容易地应用于修饰生物活性分子。一系列底物,包括紫苏醇、香茅醇、香叶醇、l -薄荷醇和胆固醇,成功地以高选择性安装到烯烃上。
{"title":"Visible‐Light Driven Copper‐Catalyzed Oxidative Alkylation of Styrenes with Sulfonium Salts and Alcohol or Acids","authors":"Long‐Jin Zhong ,&nbsp;Shu‐Zheng Ou ,&nbsp;Peng‐Fei Huang ,&nbsp;Ke‐Wen Tang ,&nbsp;Quan Zhou ,&nbsp;Yu Liu","doi":"10.1002/adsc.70314","DOIUrl":"10.1002/adsc.70314","url":null,"abstract":"<div><div>We developed a three‐component intermolecular alkoxysulfurization or estersulfurization of styrenes for the synthesis of emote alkoxy (ester) substituted thioether derivatives through copper/visible light catalyzed strategy. A variety of substrates were successfully converted into the desired sulfur‐containing products in moderate to good yields, demonstrating good functional group tolerance and excellent regioselectivity. Moreover, this method can be readily applied to modify bioactive molecules. A range of substrates, including perillyl alcohol, citronellol, geraniol, <em>L</em>‐menthol, and cholesterol, were successfully install to olefins with high selectivity.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70314"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147320089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Synergistic Photocatalytic Hydrogen Evolution of NiCeOx Bimetallic Oxide Nanosheets and Cadmium Sulfide Heterojunction NiCeO x双金属氧化物纳米片与硫化镉异质结的协同光催化析氢
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-03 Epub Date: 2025-12-24 DOI: 10.1002/adsc.70176
Xinwan Zhao , Minjun Lei , Xiaoli Ma , Zhiliang Jin
To address the rapid photogenerated carrier recombination issue that limits the efficiency of photocatalytic applications in semiconductors, this article presents for the first time the application of NiCeOx bimetallic oxides synthesized by the hydrothermal method in photocatalytic hydrogen production. By forming an S‐shaped heterojunction with cadmium sulfide (CdS) nanorods, an internal electric field is simultaneously generated to enhance the efficiency of surface carrier separation. Experimental findings reveal that the hydrogen evolution rate for NiCeOx/CdS achieves 8604.78 μmolg−1 h−1. This result indicates that the establishment of this unique heterojunction facilitates more effective electron movement from NiCeOx to CdS, leading to accelerated charge separation and transfer processes. Both experiments and theoretical calculations have jointly demonstrated that the composite material enhances the hydrogen production rate through photocatalysis and have also revealed the charge transfer mechanism of the S‐scheme heterojunction. This research provides a promising strategy for utilizing novel bimetallic oxide within the domain of photocatalysis and realizing directed electron migration in photocatalytic hydrogen evolution.
为了解决限制半导体光催化应用效率的光生载流子快速重组问题,本文首次介绍了水热法合成NiCeO x双金属氧化物在光催化制氢中的应用。通过与硫化镉(CdS)纳米棒形成S形异质结,同时产生内部电场以提高表面载流子分离的效率。实验结果表明,NiCeO x /CdS的析氢速率达到8604.78 μmolg−1 h−1。这一结果表明,这种独特异质结的建立促进了更有效的电子从NiCeO x向CdS的移动,从而加速了电荷分离和转移过程。实验和理论计算共同证明了复合材料通过光催化提高了产氢速率,并揭示了S -图式异质结的电荷转移机理。本研究为新型双金属氧化物在光催化领域的应用以及在光催化析氢过程中实现定向电子迁移提供了一种有前景的策略。
{"title":"Synergistic Photocatalytic Hydrogen Evolution of NiCeOx Bimetallic Oxide Nanosheets and Cadmium Sulfide Heterojunction","authors":"Xinwan Zhao ,&nbsp;Minjun Lei ,&nbsp;Xiaoli Ma ,&nbsp;Zhiliang Jin","doi":"10.1002/adsc.70176","DOIUrl":"10.1002/adsc.70176","url":null,"abstract":"<div><div>To address the rapid photogenerated carrier recombination issue that limits the efficiency of photocatalytic applications in semiconductors, this article presents for the first time the application of NiCeO<sub><em>x</em></sub> bimetallic oxides synthesized by the hydrothermal method in photocatalytic hydrogen production. By forming an S‐shaped heterojunction with cadmium sulfide (CdS) nanorods, an internal electric field is simultaneously generated to enhance the efficiency of surface carrier separation. Experimental findings reveal that the hydrogen evolution rate for NiCeO<sub><em>x</em></sub>/CdS achieves 8604.78 μmolg<sup>−1 </sup>h<sup>−1</sup>. This result indicates that the establishment of this unique heterojunction facilitates more effective electron movement from NiCeO<sub><em>x</em></sub> to CdS, leading to accelerated charge separation and transfer processes. Both experiments and theoretical calculations have jointly demonstrated that the composite material enhances the hydrogen production rate through photocatalysis and have also revealed the charge transfer mechanism of the S‐scheme heterojunction. This research provides a promising strategy for utilizing novel bimetallic oxide within the domain of photocatalysis and realizing directed electron migration in photocatalytic hydrogen evolution.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70176"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807526","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Cobalt‐Salen Catalysed Hydration of Alkenes With Water: A Complementary Ionic Approach to the Mukaiyama Hydration 钴- salen催化烯烃与水的水化反应:Mukaiyama水化反应的互补离子方法
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-03 Epub Date: 2026-03-07 DOI: 10.1002/adsc.70322
David G. Groves , Reece H. Hoogesteger , Balakumar Emayavaramban , Craig P. Johnston
Accessing alcohols from readily available chemical feedstocks is a critical process within synthetic methodology. The hydration of olefins is a convenient method for the introduction of an alcohol functional group, ideally via the direct addition of water across the alkene. However, current transition metal‐catalysed protocols (Mukaiyama‐type hydration) are dominated by radical addition to molecular oxygen. Ionic processes involving direct hydration with water are underexplored, yet highly desirable due to the simplicity of the reagents required. Herein, we report a cobalt‐salen catalysed hydration of alkenes proceeding via a radical–polar crossover mechanism and subsequent nucleophilic attack of water. This is a complementary protocol to previously reported radical‐based hydrations, which display analogous reactivity to traditional acid‐catalysed methods. The mild reaction conditions employed make the protocol synthetically practical and convenient for accessing alcohols from the corresponding alkenes.
从现成的化学原料中获得醇是合成方法中的一个关键过程。烯烃水合反应是引入醇官能团的一种方便方法,理想的方法是在烯烃上直接加水。然而,目前过渡金属催化的方案(mukaiyama型水化)主要是自由基加成到分子氧。涉及与水直接水合作用的离子过程尚未得到充分探索,但由于所需试剂的简单性,这是非常可取的。在这里,我们报道了一个钴盐催化的烯烃水化过程,通过自由基-极性交叉机制和随后的亲核攻击水。这是先前报道的自由基水合反应的补充方案,它显示出与传统酸催化方法类似的反应性。所采用的温和反应条件使该工艺在合成上具有实用性,并便于从相应的烯烃中得到醇。
{"title":"Cobalt‐Salen Catalysed Hydration of Alkenes With Water: A Complementary Ionic Approach to the Mukaiyama Hydration","authors":"David G. Groves ,&nbsp;Reece H. Hoogesteger ,&nbsp;Balakumar Emayavaramban ,&nbsp;Craig P. Johnston","doi":"10.1002/adsc.70322","DOIUrl":"10.1002/adsc.70322","url":null,"abstract":"<div><div>Accessing alcohols from readily available chemical feedstocks is a critical process within synthetic methodology. The hydration of olefins is a convenient method for the introduction of an alcohol functional group, ideally via the direct addition of water across the alkene. However, current transition metal‐catalysed protocols (Mukaiyama‐type hydration) are dominated by radical addition to molecular oxygen. Ionic processes involving direct hydration with water are underexplored, yet highly desirable due to the simplicity of the reagents required. Herein, we report a cobalt‐salen catalysed hydration of alkenes proceeding via a radical–polar crossover mechanism and subsequent nucleophilic attack of water. This is a complementary protocol to previously reported radical‐based hydrations, which display analogous reactivity to traditional acid‐catalysed methods. The mild reaction conditions employed make the protocol synthetically practical and convenient for accessing alcohols from the corresponding alkenes.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70322"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
Donor–Acceptor–Donor Complex Enabled, Metal‐, and Photocatalyst‐Free Synthesis of NEK2 and Cumene Oxidation Inhibitors via Direct Decarboxylative Amination of N‐Aryl Glycines 通过n -芳基甘氨酸直接脱羧胺化,供体-受体-供体复合物启用,金属和无光催化剂合成NEK2和Cumene氧化抑制剂
IF 4 2区 化学 Q2 CHEMISTRY, APPLIED Pub Date : 2026-03-03 Epub Date: 2026-03-07 DOI: 10.1002/adsc.70337
Haiyan Liu , Jianjing Yang , Qiuhong Liang , Kelu Yan , Xiangyu Wang , Jiangwei Wen
The donor–acceptor–donor (DAD) complex model provides a reliable strategy for mediating direct decarboxylative coupling between two electron donors, effectively eliminating the need for amino acid preactivation, external photocatalysts, or transition‐metal catalysts. Herein, a metal‐ and photocatalyst‐free direct decarboxylative amination has been developed through photoactive DAD complexes. This strategy enables efficient access to valuable sulfur‐containing heterocycles, including key intermediates for NEK2 inhibitors and cumene oxidation inhibitors, under mild blue‐light irradiation. Mechanistic studies confirm the formation of a DAD complex, which, upon photoexcitation, undergoes a single‐electron transfer (SET) process to generate radical species, followed by decarboxylation and selective CN coupling. The method features broad substrate scope, operational simplicity, and scalability, providing a practical and sustainable alternative to conventional photocatalytic systems.
供体-受体-供体(DAD)复合物模型为介导两个电子供体之间的直接脱羧偶联提供了一种可靠的策略,有效地消除了对氨基酸预活化、外部光催化剂或过渡金属催化剂的需要。本文通过光活性DAD配合物开发了一种无金属光催化剂的直接脱羧胺化反应。这种策略可以在轻度蓝光照射下有效地获得有价值的含硫杂环,包括NEK2抑制剂和异丙烯氧化抑制剂的关键中间体。机理研究证实了DAD复合物的形成,该复合物在光激发下经历单电子转移(SET)过程产生自由基,随后进行脱羧和选择性C - γ - N偶联。该方法具有广泛的衬底范围,操作简单,可扩展性,为传统的光催化系统提供了实用和可持续的替代方案。
{"title":"Donor–Acceptor–Donor Complex Enabled, Metal‐, and Photocatalyst‐Free Synthesis of NEK2 and Cumene Oxidation Inhibitors via Direct Decarboxylative Amination of N‐Aryl Glycines","authors":"Haiyan Liu ,&nbsp;Jianjing Yang ,&nbsp;Qiuhong Liang ,&nbsp;Kelu Yan ,&nbsp;Xiangyu Wang ,&nbsp;Jiangwei Wen","doi":"10.1002/adsc.70337","DOIUrl":"10.1002/adsc.70337","url":null,"abstract":"<div><div>The donor–acceptor–donor (DAD) complex model provides a reliable strategy for mediating direct decarboxylative coupling between two electron donors, effectively eliminating the need for amino acid preactivation, external photocatalysts, or transition‐metal catalysts. Herein, a metal‐ and photocatalyst‐free direct decarboxylative amination has been developed through photoactive DAD complexes. This strategy enables efficient access to valuable sulfur‐containing heterocycles, including key intermediates for NEK2 inhibitors and cumene oxidation inhibitors, under mild blue‐light irradiation. Mechanistic studies confirm the formation of a DAD complex, which, upon photoexcitation, undergoes a single‐electron transfer (SET) process to generate radical species, followed by decarboxylation and selective CN coupling. The method features broad substrate scope, operational simplicity, and scalability, providing a practical and sustainable alternative to conventional photocatalytic systems.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70337"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147329957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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
期刊
Advanced Synthesis & Catalysis
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
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
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术
文献互助 智能选刊 最新文献 互助须知 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 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1