Fu Ye, Juhua Li, Peiwen Liu, Gaoyu Zhao, Ye Meng, Xiaoxiang Xi, Weiming Yuan
{"title":"Nickel‐Catalyzed Regio‐ and Stereoselective Three‐Component Difunctionalization of Alkynes","authors":"Fu Ye, Juhua Li, Peiwen Liu, Gaoyu Zhao, Ye Meng, Xiaoxiang Xi, Weiming Yuan","doi":"10.1002/adsc.70850","DOIUrl":"https://doi.org/10.1002/adsc.70850","url":null,"abstract":"Nickel‐catalyzed three‐component difunctionalization of alkynes has emerged as a powerful strategy for the rapid construction of complex molecular architectures with high step and atom economy. This review systematically summarizes recent advances in alkyne difunctionalizations and categorizes them into two sections based on different catalytic modes: single nickel catalysis and photoredox/nickel dual catalysis. The single nickel catalysis exploits the intrinsic redox versatility of nickel in combination with judicious ligand design to afford high levels of regio‐ and stereocontrol and broad functional‐group tolerance. In contrast, the photoredox/nickel dual catalytic system merges visible‐light‐driven single‐electron transfer with nickel–mediated bond formation, enabling otherwise challenging radical‐type difunctionalizations under mild, room‐temperature conditions and without external reductants. The mechanistic features, substrate scope, and representative examples of each paradigm are critically discussed, with emphasis on their distinct advantages and complementarity. Finally, current limitations and prospects for future development are outlined.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"3 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292625","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}
Hoang Vu Minh Trinh, Pierrick Nun, Guillaume Dagousset, Elsa Anselmi, Emmanuel Magnier, Vincent Coeffard
{"title":"Photocascade Catalysis: Access to Arene Endoperoxides as Singlet Oxygen Batteries Through Oxyfluoroalkylation and Photooxygenation","authors":"Hoang Vu Minh Trinh, Pierrick Nun, Guillaume Dagousset, Elsa Anselmi, Emmanuel Magnier, Vincent Coeffard","doi":"10.1002/adsc.70852","DOIUrl":"https://doi.org/10.1002/adsc.70852","url":null,"abstract":"The merger of different visible light–driven reactions in one‐pot processes is a powerful strategy for constructing functionalized molecular architectures. In this context, photocascade reactions based on combinations of single‐electron transfer processes (SET–SET), sequences initiated by energy transfer followed by a photoredox step (EnT–SET), and SET–EnT processes have flourished in the literature. However, current approaches involving EnT processes are largely limited to alkene isomerizations. Herein, we report a photocascade transformation that merges photoredox oxyfluoroalkylation with oxygen sensitization via triplet–triplet energy transfer. This strategy enables the formation of functionalized arene endoperoxides from vinyl‐substituted naphthalenes and anthracenes. These endoperoxides subsequently serve as efficient sources of singlet oxygen upon thermolysis. Investigation of the substitution pattern highlights the critical role of functional groups borne by the arene framework.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292627","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}
Isabella E. E. Kroschel, Wolfgang Kroutil, Joerg H. Schrittwieser
{"title":"Multienzyme Cascade Reactions: Compatibility, Cooperativity, and Control","authors":"Isabella E. E. Kroschel, Wolfgang Kroutil, Joerg H. Schrittwieser","doi":"10.1002/adsc.70829","DOIUrl":"https://doi.org/10.1002/adsc.70829","url":null,"abstract":"Multienzyme cascades combine several biocatalytic reactions in a single synthetic operation without isolation of intermediates. Compared to traditional multistep sequences, they offer significant advantages in terms of time and resource efficiency, and they often enable overall transformations that would not be possible by performing the constituent steps independently of each other. In this review article, we highlight selected multienzyme cascades from the recent literature (mainly 2020–2025) and discuss their main benefits and challenges along three overarching themes: compatibility of the required chemical transformations and biocatalysts, cooperativity between enzymes that operate concurrently in the same vessel, and control over the final outcome of the complete reaction sequence. Cascade designs that account for these aspects have enabled the expedient synthesis of a broad range of relevant target compounds, including complex pharmaceutical drugs prepared on industrial scale.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"84 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292626","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}
Sheila G. Perez Edighill, Damian E. Yerien, Sebastian Barata‐Vallejo, Al Postigo
{"title":"A General Red‐Light Photocatalytic Platform for the Synthesis of Perfluoroalkyl Tellanes","authors":"Sheila G. Perez Edighill, Damian E. Yerien, Sebastian Barata‐Vallejo, Al Postigo","doi":"10.1002/adsc.70833","DOIUrl":"https://doi.org/10.1002/adsc.70833","url":null,"abstract":"Perfluoroalkyl tellanes (R <jats:sub>F</jats:sub> –Te–R) constitute a synthetically valuable yet underdeveloped class of organotellurium compounds, despite their potential in fluoroorganic chemistry and materials science. Herein, we disclose a general, efficient, and operationally simple photocatalytic strategy for their synthesis from readily available ditellanes and perfluoroalkyl iodides. The transformation is enabled by red‐light irradiation in the presence of zinc phthalocyanine as an inexpensive and readily accessible photocatalyst, allowing the generation of perfluoroalkyl radicals under exceptionally mild conditions. This protocol exhibits broad substrate scope, accommodating a wide range of diaryl, heteroaryl, and dialkyl ditellanes, including sterically congested and biologically relevant scaffolds, and consistently delivers the corresponding perfluoroalkyl tellanes in high yields. Mechanistic studies, including radical trapping experiments, Stern–Volmer analysis, and quantum yield determination ( <jats:italic>Φ </jats:italic> = 2.4), reveal a photoinitiated radical chain mechanism in which the inherent lability of the Te─Te bond plays a key role in facilitating efficient radical capture and propagation. By combining low‐energy photochemical activation with the unique reactivity of tellurium‐centered species, this work establishes a practical and scalable platform for C─Te bond formation and significantly expands the synthetic toolbox for accessing perfluoroalkyl tellanes.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"61 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292645","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}
{"title":"Para ‐Selective C─H Amination of Benzenepropanamides via Photocatalytic N ‐Centered Radical‐Mediated Dearomatization","authors":"Di‐Jing Luo, Dan‐Na Chen, Li‐Ning Chen, Lu‐Lu Qin, Yu Lv, Zhi‐Peng Ye, Yu Zheng, Shu‐Hui Li, Peng‐Ju Xia","doi":"10.1002/adsc.70851","DOIUrl":"https://doi.org/10.1002/adsc.70851","url":null,"abstract":"We report a photocatalytic strategy for constructing <jats:italic>para</jats:italic> ‐aminobenzenepropanamide scaffolds. This method employs oxime‐ester‐based diamination reagents as dual‐radical precursors to generate imino and amidyl radicals. The key step involves <jats:italic>N</jats:italic> ‐centered radical‐mediated intramolecular dearomatization, forming the cyclohexadienyl radical (CHDR) intermediate. This protocol features mild reaction conditions and broad functional group tolerance. Furthermore, this method achieves selectivity that is not affected by the stereochemical or electronic properties of the benzene ring, thereby enabling the efficient synthesis of 4‐aminobenzoylamide.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"34 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292650","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}
Zhe Huang, Shangyong Wu, Zhaojun Ding, Xiyu Luo, Zihao Lin, Shi Zang, Na Wu, Jiayu Mo
{"title":"Photoelectrochemically Driven Hydrophosphorylation of Alkynes to Access ( E )‐Alkenylphosphine Oxides","authors":"Zhe Huang, Shangyong Wu, Zhaojun Ding, Xiyu Luo, Zihao Lin, Shi Zang, Na Wu, Jiayu Mo","doi":"10.1002/adsc.70837","DOIUrl":"https://doi.org/10.1002/adsc.70837","url":null,"abstract":"The current metal‐free methods for the hydrophosphorylation of alkynes, encompassing both electrochemical‐driven and photoredox‐catalyzed processes separately, show efficacy only when applied to less hindered terminal alkynes, polarized internal alkynes, or aryl alkyl internal alkynes; diaryl acetylenes are found to be incompatible with these conditions. Both methods involve a radical stepwise addition, yielding a <jats:italic>Z</jats:italic> / <jats:italic>E</jats:italic> isomeric mixture with the <jats:italic>Z</jats:italic> ‐alkenylphosphine oxides as the primary products. Furthermore, electrochemical hydrophosphorylation of alkynes is prone to double reduction of alkynes during extended reaction times. Herein, in sharp contrast to conventional, often separate, electrochemical or photoredox catalytic approaches that typically produce a <jats:italic>Z</jats:italic> / <jats:italic>E</jats:italic> isomeric mixture, this photoelectrocatalytic (PEC) process, which combines photocatalysis and electrochemistry, exclusively furnishes stereospecific ( <jats:italic>E</jats:italic> )‐alkenylphosphine oxides as the sole products. Significantly, this protocol successfully applies efficiently to diaryl acetylenes and bulky terminal alkynes, with no iterative addition of triple bonds observed.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"84 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292653","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}
{"title":"Application of Bifunctional Togni’s Reagent in Photoredox‐Catalyzed Oxytrifluoromethylation of Alkenes","authors":"Xiaoyu Wang, Ronghui Zhang, Yuyang Xue, Yichen Tao, Sixu Yang, Lin Tang","doi":"10.1002/adsc.70844","DOIUrl":"https://doi.org/10.1002/adsc.70844","url":null,"abstract":"We report a radical‐based protocol for the photoredox‐catalyzed oxytrifluoromethylation of alkenes with Togni’s reagent. This strategy provides efficient access to a broad array of CF <jats:sub>3</jats:sub> ‐containing esters and is also applicable to late‐stage functionalization of drug molecules under mild conditions. Moreover, conversion of the resulting CF <jats:sub>3</jats:sub> ‐functionalized esters to other valuable building blocks is also achieved. Mechanistic investigations reveal that Togni’s reagent acts as both a trifluoromethyl and an acyloxy group. Consequently, the difunctionalization reaction can proceed without any external nucleophiles, offering high atom economy.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292659","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}
Yang Zhang, Yating Wang, Conghui Wang, Meizhong Tang, Lan‐Gui Xie
{"title":"Multicomponent Reactions Enabled by Photoinduced Formal Alkyl Transfer of Tertiary Amines","authors":"Yang Zhang, Yating Wang, Conghui Wang, Meizhong Tang, Lan‐Gui Xie","doi":"10.1002/adsc.70846","DOIUrl":"https://doi.org/10.1002/adsc.70846","url":null,"abstract":"Multicomponent reactions (MCRs) provide a powerful and efficient strategy for rapidly accessing structurally diverse compounds under mild conditions. Among MCRs, the Ugi‐type reactions—including the Ugi–azide variant—hold a central role in the synthesis of α‐amino derivatives. Historically, research in this area has largely focused on expanding the scope of nucleophiles to access novel and complex products. However, most reported transformations still rely on imine (or iminium) intermediates generated from primary/secondary amines and aldehydes/ketones. In this work, we disclose a photochemical approach that utilizes photoexcited aromatic amines to trigger the oxidation of tertiary amines, leading to the formation of iminium species. These intermediates undergo a formal alkyl transfer process with aromatic amines to generate new iminium salts, which subsequently engage with various nucleophiles in a multicomponent fashion. This strategy enables the efficient synthesis of three important classes of functional molecules—α‐amino phosphine oxides, tetrazoles, and imides—via a tertiary amine‐involved MCR under light irradiation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292646","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}
{"title":"Influence of Supports on Electrocatalytic Performance of Dual‐Atom Catalysts","authors":"Pan Zhou, Tieli Zhou, Jingqi Guan","doi":"10.1002/adsc.70840","DOIUrl":"https://doi.org/10.1002/adsc.70840","url":null,"abstract":"Due to excellent atomic usage, stability, activity, and selectivity, dual‐atom catalysts (DACs) have attracted a lot of attention in electrocatalysis. The dispersion, electrical structure, stability, and catalytic reaction dynamics of the functional sites are all directly influenced by the chemical and physical properties of the supports, including specific surface area, pore structure, conductivity, and surface chemical state. Here, the support categorization and structure design of DACs are examined. To expedite the development of high‐performance DACs and uncover the structure–performance relationship, a sensible modulation technique is subsequently put out. Furthermore, the dynamic evolution of diatomic sites during the electrocatalytic processes is demonstrated using sophisticated characterization techniques. Afterward, the applications of DACs in energy conversion devices and electrocatalysis are examined. Finally, the potential and problems associated with the continued development of DACs for energy‐related applications are presented.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"46 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292685","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}
Tomáš Čarný, Barbora Steinhüblová, Maksym Ponedilok, Radovan Šebesta
{"title":"Ball‐Milling‐Enabled Pd‐Catalyzed One‐Pot Cross‐Coupling of Aryl Thianthrenium Salts With In Situ Generated Reformatsky Enolates","authors":"Tomáš Čarný, Barbora Steinhüblová, Maksym Ponedilok, Radovan Šebesta","doi":"10.1002/adsc.70853","DOIUrl":"https://doi.org/10.1002/adsc.70853","url":null,"abstract":"Mechanochemistry enables an efficient Pd‐catalyzed cross‐coupling of aryl thianthrenium salts with in situ generated Reformatsky‐type enolates. Ball milling plays a dual role by promoting both the activation of zinc to form Reformatsky‐type organozinc enolates from <jats:italic>α</jats:italic> ‐halo esters and amides and their subsequent cross‐coupling with solid aryl thianthrenium salts. This single‐step one‐pot protocol provides access to a broad range of <jats:italic>α</jats:italic> ‐arylated products in high yields within short reaction times. The mechanochemical process is performed under ambient conditions without requiring an inert atmosphere, highlighting its operational simplicity and practicality. Furthermore, the methodology is readily applicable to the late‐stage functionalization of structurally complex bioactive molecules.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149292546","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}