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.
{"title":"Machine Learning Guided d-Orbital Electron Modulated Graphene-Based Catalysts for Enhanced Electrochemical Ammonia Synthesis","authors":"Gengwei Wu, Yusen Du, Yan Zhuang, Ying Wang, Yujing Lv, Rui Chen, Zhengxin Ding, Rusheng Yuan, Zizhong Zhang, Jinlin Long","doi":"10.1002/adsc.70343","DOIUrl":"https://doi.org/10.1002/adsc.70343","url":null,"abstract":"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.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"14 1","pages":""},"PeriodicalIF":5.4,"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}
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.
{"title":"Recent Developments in Transition-Metal-Catalyzed Tandem C?H Activation/Cyclization of α,ω-Diynes","authors":"Fen Xu, Jia-Qi Huo, Ya-Peng Li, Fan-Wang Zeng, Shi-Yu Zhang, Yuan Feng, Luciano Barboni","doi":"10.1002/adsc.70339","DOIUrl":"https://doi.org/10.1002/adsc.70339","url":null,"abstract":"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.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"54 1","pages":""},"PeriodicalIF":5.4,"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}
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.
{"title":"Recent Progress in Asymmetric Oxidative Radical–Polar Crossover Reactions","authors":"Xiaochong Guo, Kangping Wu, Mianling Zhang","doi":"10.1002/adsc.70315","DOIUrl":"https://doi.org/10.1002/adsc.70315","url":null,"abstract":"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.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"44 1","pages":""},"PeriodicalIF":5.4,"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}
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.
{"title":"Mechanochemical Synthesis of N, N-Disubstituted 2-Amino-Thiazolines, and 1,3-Thiazolidine-2-Imine Hydrochlorides","authors":"Kamil Hanek, Barbara Kaczmarek, Dawid Frąckowiak, Patrycja Żak","doi":"10.1002/adsc.70340","DOIUrl":"https://doi.org/10.1002/adsc.70340","url":null,"abstract":"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.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"6 1","pages":""},"PeriodicalIF":5.4,"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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70242
Kate Andersen , Nora Struchtrup , Adam Sylvain‐Stewart , Liliia Pestereva , Benjamin Godwin , Gino A. DiLabio , Jeremy E. Wulff
Trifluoromethyl aryl diazirines are ubiquitous in chemical biology applications, and are increasingly used in materials science. While the electron‐withdrawing α‐CF3 group is known to stabilize the carbene resulting from diazirine activation, no alternative electron‐withdrawing groups have been systematically studied. Here, we describe the synthesis of the first α‐ester aryl diazirines and show that they activate at lower temperatures than their trifluoromethyl‐containing analogs, while still permitting tunable activation and good efficiency in CH insertion reactions. We anticipate the use of α‐ester aryl diazirines in materials science applications (due to their high insertion yield with a nonfunctionalized aliphatic model substrate) and biological wound healing (due to their ability to be thermally activated at < 37°C).
{"title":"Alpha‐Ester Aryl Diazirines: Low‐Temperature Carbene Progenitors for Materials Applications","authors":"Kate Andersen , Nora Struchtrup , Adam Sylvain‐Stewart , Liliia Pestereva , Benjamin Godwin , Gino A. DiLabio , Jeremy E. Wulff","doi":"10.1002/adsc.70242","DOIUrl":"10.1002/adsc.70242","url":null,"abstract":"<div><div>Trifluoromethyl aryl diazirines are ubiquitous in chemical biology applications, and are increasingly used in materials science. While the electron‐withdrawing <em>α</em>‐CF<sub>3</sub> group is known to stabilize the carbene resulting from diazirine activation, no alternative electron‐withdrawing groups have been systematically studied. Here, we describe the synthesis of the first <em>α</em>‐ester aryl diazirines and show that they activate at lower temperatures than their trifluoromethyl‐containing analogs, while still permitting tunable activation and good efficiency in CH insertion reactions. We anticipate the use of <em>α</em>‐ester aryl diazirines in materials science applications (due to their high insertion yield with a nonfunctionalized aliphatic model substrate) and biological wound healing (due to their ability to be thermally activated at < 37°C).</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70242"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146260853","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70307
Wei Rao , Yifan Jiang , Qiong Liu , Junjun Zhang , Die He , Rong Chen
While high‐valent copper intermediates are pivotal for efficient peroxydisulfate (PDS) activation, their generation and role in heterogeneous catalysis remain unclear. Herein, we demonstrate that a nonstoichiometric Cu0.84Bi2.08O4 catalyst enables the dark activation of PDS via a novel pathway dominated by a surface‐bound Cu(III)‐peroxo intermediate (≡Cu(III)‐O−O−SO3). A suite of spectroscopic and chemical probes revealed that this Cu(III)‐peroxo species, along with superoxide radicals (•O2−), acts as the primary oxidant, enabling the highly selective and rapid degradation of bisphenol A (BPA) and other phenolic pollutants. Furthermore, H2O2 generated from PDS hydrolysis synergistically participates in the reaction, accounting for the exceptionally high PDS utilization efficiency of the system. The system exhibits remarkable robustness, maintaining high activity over a wide pH range (4–11) and demonstrating strong resistance to interference from ions. This study elucidates a distinct Cu(III)‐peroxo‐mediated mechanism and offers a new strategy for designing highly selective catalysts for environmental remediation.
{"title":"Nonstoichiometric Copper Bismuth Oxide Catalyst Boosting Surface‐Bound Cu(III)‐Peroxo Intermediate for Selective Oxidation via Dark Peroxydisulfate Activation","authors":"Wei Rao , Yifan Jiang , Qiong Liu , Junjun Zhang , Die He , Rong Chen","doi":"10.1002/adsc.70307","DOIUrl":"10.1002/adsc.70307","url":null,"abstract":"<div><div>While high‐valent copper intermediates are pivotal for efficient peroxydisulfate (PDS) activation, their generation and role in heterogeneous catalysis remain unclear. Herein, we demonstrate that a nonstoichiometric Cu<sub>0.84</sub>Bi<sub>2.08</sub>O<sub>4</sub> catalyst enables the dark activation of PDS via a novel pathway dominated by a surface‐bound Cu(III)‐peroxo intermediate (<strong>≡</strong>Cu(III)‐O−O−SO<sub>3</sub>). A suite of spectroscopic and chemical probes revealed that this Cu(III)‐peroxo species, along with superoxide radicals (•O<sub>2</sub><sup>−</sup>), acts as the primary oxidant, enabling the highly selective and rapid degradation of bisphenol A (BPA) and other phenolic pollutants. Furthermore, H<sub>2</sub>O<sub>2</sub> generated from PDS hydrolysis synergistically participates in the reaction, accounting for the exceptionally high PDS utilization efficiency of the system. The system exhibits remarkable robustness, maintaining high activity over a wide pH range (4–11) and demonstrating strong resistance to interference from ions. This study elucidates a distinct Cu(III)‐peroxo‐mediated mechanism and offers a new strategy for designing highly selective catalysts for environmental remediation.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70307"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319850","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70348
Yuping Wu , Xinyu Du , Yaoguo Wang , Zixin Feng , YunRu Ma , Yingying Fan , Li Niu
Constructing polymer photocatalysts that can concurrently accomplish charge transfer and mass transport to catalytic sites remains a formidable task. In this study, by cross‐linking electron‐rich polyphenol and electron‐poor phenothiazine units, two hydrophilic and porous organic polymer photocatalysts characterized by densely packed donor–acceptor units are deliberately designed. The hydrophilic phenolic hydroxyl group in the donor moiety and the aperture channel neighboring the acceptor unit facilitate the capture of water and oxygen at the catalytic site. Meanwhile, the donor–acceptor columns serve as charge supply chains and numerous water oxidation and oxygen reduction centers. These photocatalysts are used for the photocatalytic synthesis of hydrogen peroxide from water and oxygen without the use of sacrificial reagents. Therein, the polymer containing tetramethyl groups shows high selectivity for the photogeneration of hydrogen peroxide, achieving a yield rate of 691.3 μmol g−1 h−1 (16.73 mM g−1) and an apparent quantum yield (AQY) of 11.9% under 630 nm irradiation. This organic polymer catalyst system exhibits considerable potential as a promising artificial photosynthesis system capable of realizing simultaneous charge transfer and mass transfer.
构建能够同时完成电荷转移和质量传递到催化位点的聚合物光催化剂仍然是一项艰巨的任务。在这项研究中，通过交联富电子多酚和贫电子吩噻嗪单元，故意设计了两种亲水性和多孔的有机聚合物光催化剂，其特征是密集排列的供体-受体单元。供体部分的亲水酚羟基和邻近受体单元的孔径通道有助于在催化位点捕获水和氧。同时，供体-受体柱作为电荷供应链和众多的水氧化和氧还原中心。这些光催化剂用于水和氧的光催化合成过氧化氢，而不使用牺牲试剂。其中，含四甲基的聚合物对过氧化氢的光生成表现出较高的选择性，在630 nm辐照下的产率为691.3 μmol g−1 h−1 (16.73 mM g−1)，表观量子产率（AQY）为11.9%。该有机聚合物催化剂体系作为一种有潜力的人工光合作用体系，能够同时实现电荷传递和质量传递。
{"title":"Organic Polymers Enabling Concurrent Charge and Mass Transfer for Photocatalytic Hydrogen Peroxide Synthesis","authors":"Yuping Wu , Xinyu Du , Yaoguo Wang , Zixin Feng , YunRu Ma , Yingying Fan , Li Niu","doi":"10.1002/adsc.70348","DOIUrl":"10.1002/adsc.70348","url":null,"abstract":"<div><div>Constructing polymer photocatalysts that can concurrently accomplish charge transfer and mass transport to catalytic sites remains a formidable task. In this study, by cross‐linking electron‐rich polyphenol and electron‐poor phenothiazine units, two hydrophilic and porous organic polymer photocatalysts characterized by densely packed donor–acceptor units are deliberately designed. The hydrophilic phenolic hydroxyl group in the donor moiety and the aperture channel neighboring the acceptor unit facilitate the capture of water and oxygen at the catalytic site. Meanwhile, the donor–acceptor columns serve as charge supply chains and numerous water oxidation and oxygen reduction centers. These photocatalysts are used for the photocatalytic synthesis of hydrogen peroxide from water and oxygen without the use of sacrificial reagents. Therein, the polymer containing tetramethyl groups shows high selectivity for the photogeneration of hydrogen peroxide, achieving a yield rate of 691.3 μmol g<sup>−1</sup> h<sup>−1</sup> (16.73 mM g<sup>−1</sup>) and an apparent quantum yield (AQY) of 11.9% under 630 nm irradiation. This organic polymer catalyst system exhibits considerable potential as a promising artificial photosynthesis system capable of realizing simultaneous charge transfer and mass transfer.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70348"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319851","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70321
Zhenlei Zhang , Manqi Zhang , Wei Zhao , Jun Yu , Xiaozheng Li , Ruisong Shi , Jiajun Zheng
We present a method for the selective synthesis of thiochromanes and allyl sulfides that is both metal‐ and oxidant‐free. This method uses 2‐methylquinoline or acetophenone, paraformaldehyde, and thiols as substrates. Varying the thiol substrates allows for the controlled synthesis of either thiochromanes or allyl sulfides. This protocol uses HCl as a promoter, providing an easy, efficient way to produce these sulfur‐containing compounds. Mechanistic studies suggest that the transformation proceeds via a Mannich‐type reaction pathway.
{"title":"Substrate‐Guided Divergent Synthesis of Thiochromanes and Allyl Sulfides via a Mannich‐Type Reaction","authors":"Zhenlei Zhang , Manqi Zhang , Wei Zhao , Jun Yu , Xiaozheng Li , Ruisong Shi , Jiajun Zheng","doi":"10.1002/adsc.70321","DOIUrl":"10.1002/adsc.70321","url":null,"abstract":"<div><div>We present a method for the selective synthesis of thiochromanes and allyl sulfides that is both metal‐ and oxidant‐free. This method uses 2‐methylquinoline or acetophenone, paraformaldehyde, and thiols as substrates. Varying the thiol substrates allows for the controlled synthesis of either thiochromanes or allyl sulfides. This protocol uses HCl as a promoter, providing an easy, efficient way to produce these sulfur‐containing compounds. Mechanistic studies suggest that the transformation proceeds via a Mannich‐type reaction pathway.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70321"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146215814","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70317
Jinge Gui , Yingzi Wang , Xiaofei Xie , Zhibo Zhang , Siliang You , Yingguang Zhu , Kang Chen
A photoredox/Ti dual‐catalyzed deoxygenative coupling reaction between Morita–Baylis–Hillman acetates and unprotected cycloketone oximes has been developed. A broad range of cyano‐containing trisubstituted alkenes have been expediently synthesized in good chemo‐ and stereo‐selectivities under very mild conditions. Mechanistic experiments, scale‐up reaction, and functionalization of complex molecules were conducted, in order to showcase the mechanistic features and robustness of this protocol.
{"title":"Deoxygenative Coupling Between Morita–Baylis–Hillman Acetates and Unprotected Cycloketone Oximes Enabled by Photoredox/Ti Dual Catalysis","authors":"Jinge Gui , Yingzi Wang , Xiaofei Xie , Zhibo Zhang , Siliang You , Yingguang Zhu , Kang Chen","doi":"10.1002/adsc.70317","DOIUrl":"10.1002/adsc.70317","url":null,"abstract":"<div><div>A photoredox/Ti dual‐catalyzed deoxygenative coupling reaction between Morita–Baylis–Hillman acetates and unprotected cycloketone oximes has been developed. A broad range of cyano‐containing trisubstituted alkenes have been expediently synthesized in good chemo‐ and stereo‐selectivities under very mild conditions. Mechanistic experiments, scale‐up reaction, and functionalization of complex molecules were conducted, in order to showcase the mechanistic features and robustness of this protocol.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70317"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146260851","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}
Pub Date : 2026-03-03Epub Date: 2026-03-07DOI: 10.1002/adsc.70294
Jie Yang , Jing Xie , Daohong Yu , Wenjun Luo , Jinbin Zhu , Lipeng Long , Haiqing Luo , Wei Guo , Zhongxia Wang , Zhengwang Chen
A visible‐light‐driven, photocatalyst‐free 6π‐photocyclization of N‐substituted dieneamines has been developed. Various polysubstituted cyanodihydropyrroles and cyanopyrroles were constructed in good‐to‐excellent yields under nitrogen or air atmosphere. This novel strategy features formal hydroalkenylation, divergent synthesis, excellent regioselectivity, wide functional group tolerance, and operational convenience. Mechanistic studies suggest that both the 1,4‐H shift of the diradical intermediate and the deprotonation/protonation processes may be involved in the transformation.
{"title":"Photocatalyst‐Free, Visible Light‐Driven 6π‐Photocyclization: A Facile Access to Multisubstituted Cyanodihydropyrroles and Cyanopyrroles","authors":"Jie Yang , Jing Xie , Daohong Yu , Wenjun Luo , Jinbin Zhu , Lipeng Long , Haiqing Luo , Wei Guo , Zhongxia Wang , Zhengwang Chen","doi":"10.1002/adsc.70294","DOIUrl":"10.1002/adsc.70294","url":null,"abstract":"<div><div>A visible‐light‐driven, photocatalyst‐free 6π‐photocyclization of <em>N</em>‐substituted dieneamines has been developed. Various polysubstituted cyanodihydropyrroles and cyanopyrroles were constructed in good‐to‐excellent yields under nitrogen or air atmosphere. This novel strategy features formal hydroalkenylation, divergent synthesis, excellent regioselectivity, wide functional group tolerance, and operational convenience. Mechanistic studies suggest that both the 1,4‐H shift of the diradical intermediate and the deprotonation/protonation processes may be involved in the transformation.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"368 5","pages":"Article e70294"},"PeriodicalIF":4.0,"publicationDate":"2026-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147287332","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：