Aleksandra Szymańska , Mateusz Nowicki , Subhabrata De , Barbara Krupa , Jakub Szyling , Katarina Ležaić , Marc‐Etienne Moret , Jędrzej Walkowiak
{"title":"Catalytic Hydroboration of Ketones Using Mn(CO)5Br and Mn2(CO)10","authors":"Aleksandra Szymańska , Mateusz Nowicki , Subhabrata De , Barbara Krupa , Jakub Szyling , Katarina Ležaić , Marc‐Etienne Moret , Jędrzej Walkowiak","doi":"10.1002/adsc.70092","DOIUrl":"10.1002/adsc.70092","url":null,"abstract":"<div><div>The commercially available and easy‐to‐handle manganese complexes Mn(CO)<sub>5</sub>Br and Mn<sub>2</sub>(CO)<sub>10</sub> effectively catalyze the hydroboration of ketones under mild conditions, yielding secondary alcohols after hydrolysis. These simple catalysts exhibit broad tolerance to different functional groups including esters, halides, and nitroarenes. Moreover, the reaction proceeds with high chemoselectivity toward CO bonds in the presence of esters, nitriles, nitro groups, or double CC bond. The proposed procedure enables fast, efficient synthesis of O‐borylated products, which are easily hydrolyzed in a one‐pot manner to various aryl and alkyl alcohols (even unsaturated ones) in excellent yields. Thus, the developed procedure compares favorably with other Mn catalytic systems, which require lengthy preparation, the application of structurally and electronically advanced ligands, and oxygen‐ and moisture‐free conditions.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70092"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915959","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":"Visible Light‐Driven Photoredox Carboarylation of N‐Acryloyl Phosphinimides with Sulfoxonium Ylides","authors":"Ning Xian , Huawen Huang","doi":"10.1002/adsc.70095","DOIUrl":"10.1002/adsc.70095","url":null,"abstract":"<div><div>A mild visible light‐driven photoredox cascade radical cyclization of <em>N</em>‐acryloyl phosphinamides with sulfoxonium ylides for the modular synthesis of value‐added cyclic phosphinamides under additive‐free conditions has been reported. This scalable protocol uses sulfoxonium ylides as novel carbon radical precursors in an eco‐friendly MeCN/H<sub>2</sub>O solvent system, eliminating the need for stoichiometric oxidants or bases while maintaining broad functional group tolerance. The carboarylation reaction has been successfully implemented at ambient temperature, providing an efficient and viable access to P–N scaffolds bearing a quaternary carbon center. Mechanistic studies support a proton‐coupled electron transfer pathway for radical generation from sulfoxonium ylides under visible‐light irradiation.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70095"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910717","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":"Lewis Acid‐Catalyzed Tandem Cyclizations of 1,2‐Diarylalkenols","authors":"Arnaud Espied , Djamila Azrou , Régis Guillot , Aurélien Alix , Vincent Gandon , Christophe Bour","doi":"10.1002/adsc.70065","DOIUrl":"10.1002/adsc.70065","url":null,"abstract":"<div><div>The synthesis of medium‐sized carbocycles from linear chains is challenging in organic chemistry. Among the effective methods for the synthesis of polysubstituted carbocycles with contiguous stereogenic centers, the dehydrative cyclization of alcohols with alkenes is an attractive protocol as it uses readily available substrates, without requiring unnecessary prefunctionalization, and generates water as the sole byproduct. Herein, a dehydrative cyclization reaction is explored, as well as two tandem reactions initiated by this cyclization. These reactions are allowed by metal‐based or organic Lewis acids as catalysts containing only main group elements, which proved compatible with the formation of water during the reaction. This approach allowed the synthesis of 26 new carbocycles with yields up to 97% and high diastereoselectivity.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70065"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135469","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}
Bo Yang , Bai‐Chuan Ding , Zhi‐Ao Tian , Jian‐Ping Qu , Yan‐Biao Kang
{"title":"Phenothiazinium as Metal‐Free CH Arylation Reagent for Unactivated Arenes","authors":"Bo Yang , Bai‐Chuan Ding , Zhi‐Ao Tian , Jian‐Ping Qu , Yan‐Biao Kang","doi":"10.1002/adsc.70098","DOIUrl":"10.1002/adsc.70098","url":null,"abstract":"<div><div>The construction of (hetero)biaryls plays a crucial role in chemical science, with applications in pharmaceuticals, agrochemicals, natural products, and organic materials. While aryl sulfonium salts (aryl thianthrenium‐salts and aryl DBT‐salts) have provided access to (hetero)biaryls, these methods typically require photocatalysts or transition metals to activate the reagents. Herein, a mild, visible light‐mediated, transition metal‐free, and catalyst‐free arylation of arenes using aryl phenothiazinium salts as dual functional reagents is reported. A variety of biaryls and heterobiaryls are obtained in moderate to high yields.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70098"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910718","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}
Long‐wei Lou , Juan Zhang , Lei Zhang , Shan‐ling Li , Zhi‐min Li , Zong‐lin Li
{"title":"Engineering Phosphoenolpyruvate Carboxylase with Improved Activity and Stability for High‐Efficiency Carbon Dioxide Fixation","authors":"Long‐wei Lou , Juan Zhang , Lei Zhang , Shan‐ling Li , Zhi‐min Li , Zong‐lin Li","doi":"10.1002/adsc.70052","DOIUrl":"10.1002/adsc.70052","url":null,"abstract":"<div><div>The extraction of excess CO<sub>2</sub> from the environment requires favorable carbon sequestration methods, among which biochar sequestration is one of the most effective approaches. Therefore, to meet the growing demand for high‐efficiency carbon fixation and enhanced metabolic flux in biological carbon sequestration, the development of high‐performance phosphoenolpyruvate carboxylase (PEPC) is of significant importance. In this study, a high‐activity PEPC from <em>Cannabis sativa</em> (CsPEPC) is identified. However, the enzyme exhibits poor thermal stability, with a half‐life of only 13 min at 50 °C. To improve CsPEPC performance, diverse strategies, including molecular dynamics, FoldX energy calculations, and PROSS‐based prediction, are integrated to screen beneficial variants. The resulting mutant CsPEPC<sup>C886R</sup> shows a twofold increase in activity (249.2 U mg<sup>–</sup><sup>1</sup> at 50 °C) and fivefold greater stability. Furthermore, the addition of 25% glycerol as a protein stabilizer significantly extends the half‐life of CsPEPC<sup>C886R</sup> by 31‐fold, ultimately increasing the half‐life to 2178 min. In vitro production experiments show that the optimal mutant CsPEPC<sup>C886R</sup> generates 116.8 mM oxaloacetate within 270 min. This work provides a promising PEPC variant for biological CO<sub>2</sub> fixation, which holds great potential for improving carbon assimilation and supports the development of efficient, carbon‐neutral biosynthetic pathways.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70052"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144850957","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}
Shaotong Qiu , Jiangan Liu , Dan Tang , Yangxin Mao , Zhicheng Yang , Changyuan Zhang , Hu Zhou
{"title":"Zn‐Catalyzed Cycloisomerization/Methylenation of Enyone with Vinyl Azide: Assembly of Terminal and Deuterated Alkenyl Furan Framework","authors":"Shaotong Qiu , Jiangan Liu , Dan Tang , Yangxin Mao , Zhicheng Yang , Changyuan Zhang , Hu Zhou","doi":"10.1002/adsc.70112","DOIUrl":"10.1002/adsc.70112","url":null,"abstract":"<div><div>An unprecedented zinc‐catalyzed cycloisomerization/methylenation reaction of enynone with vinyl azide is developed. Featuring inexpensive, less‐toxic catalyst, high efficiency, and mild reaction conditions, this protocol provides a practical synthetic method to access various bioactivity‐related terminal and deuterated alkenyl furans in up to 99% yield and 94% level of deuterium incorporation. The reaction is proposed to proceed through cycloisomerization, cyclopropanation, and ring fragmentation processes. Utility of this reaction is further demonstrated by transformation of the obtained molecules into selectively semi‐deuterated and non‐deuterated furan skeletons.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70112"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145035564","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}
Yaxin Wang , Zitong Hao , Muhammad Islam , Yumei Zhu , Yang Chao , Sidharam P. Pujari , Hongxia Zhao , Han Zuilhof
{"title":"SuFEx Reactions When Shaken Not Stirred","authors":"Yaxin Wang , Zitong Hao , Muhammad Islam , Yumei Zhu , Yang Chao , Sidharam P. Pujari , Hongxia Zhao , Han Zuilhof","doi":"10.1002/adsc.70081","DOIUrl":"10.1002/adsc.70081","url":null,"abstract":"<div><div>Click reactions display many of the goals desired for more sustainable chemical conversions. Yet, the solvent used is an often overlooked aspect in determining the environmental impact of reactions. In the current paper, the first mechanochemical method is developed for the efficient and solvent‐free SuFEx reaction of sulfonyl fluorides with a wide range of phenols. After outlining the optimization process, which yields an easy‐to‐use and robust method. The broad scope of this approach is evidenced, and demonstrate this potential via the application to a range of natural phenols that also display other functionalities, and several gram‐scale syntheses.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70081"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135470","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":"Synthesis of Amidines Via P(III)/P(V)O Redox Catalyzed In Situ Formation of Imidoyl Chlorides From Amides","authors":"Viktorija Medvarić , Jan Paradies , Thomas Werner","doi":"10.1002/adsc.70059","DOIUrl":"10.1002/adsc.70059","url":null,"abstract":"<div><div>Amidines are a ubiquitous class of bioactive compounds found in a wide variety of natural products; thus, efficient strategies for their preparation are in great demand. Herein, a novel protocol is reported for the synthesis of amidines based on P<sup>III</sup>/P<sup>V</sup>O redox catalysis. This two‐step, one‐pot approach involves the activation of amides via P<sup>III</sup>/P<sup>V</sup>O catalyzed in situ formation of imidoyl chloride intermediates which are directly converted upon reaction with amines into the corresponding amidines. Instead of traditionally used toxic and corrosive chloride sources, hexachloroacetone (HCA) is successfully employed as a halide source. The reaction proceeds with low catalyst loading (2 mol%) in BuOAc as the solvent. Under the optimized conditions, 20 amidines are prepared in yields up to 99%. A feasible mechanism is proposed based on experimental results. The synthetic potential of this method is evaluated in the preparation of the tyrosine kinase inhibitor (TKI) Erlotinib.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70059"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915955","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}
Anirban Chowdhury , Akkammagari Putta Rangappa , Wenhua Xue , Yixuan Liu , Jun Zhao
{"title":"Facet‐Engineered Cds with Cd Vacancies for High‐Efficiency Photocatalytic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Diformylfuran","authors":"Anirban Chowdhury , Akkammagari Putta Rangappa , Wenhua Xue , Yixuan Liu , Jun Zhao","doi":"10.1002/adsc.70093","DOIUrl":"10.1002/adsc.70093","url":null,"abstract":"<div><div>The photocatalytic oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) is a promising process with significant implications for sustainable energy and environmental applications. However, achieving highly selective DFF production from HMF remains a challenging task, particularly due to the dependency of molecular O<sub>2</sub> activation on the composition and exposed facets of nanomaterials. This study investigates the impact of different preferential facets of hydrothermally synthesized cadmium sulfide (CdS) morphologies—including hollow spheres, nanorods, and flower‐like structures—on the photocatalytic oxidation of HMF to DFF. The findings reveal that the preferential CdS (002) facet and Cd vacancies in the hollow sphere morphology significantly enhance photocatalytic activity, achieving 68% HMF conversion and 89% selectivity for DFF production within 12 h of reaction time. This work highlights the critical role of material composition and facet orientation in optimizing photocatalytic processes for selective oxidation reactions, offering a potential strategy for the design of advanced photocatalysts in sustainable chemical production.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70093"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145035563","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":"N‐Heterocyclic Carbenes (NHCs): An Emerging Efficient Catalyst in Amide Bond Formation","authors":"Ashmita Singh , Aashish , Anudeep K. Narula , Ismail Althagafi , Ramendra Pratap","doi":"10.1002/adsc.70036","DOIUrl":"10.1002/adsc.70036","url":null,"abstract":"<div><div>Since the discovery of N‐heterocyclic carbenes (NHCs), their role as ligands and organocatalysts has grown significantly due to their unique umpolung reactivity and strong <em>σ</em>‐donor capabilities. In recent years, the field of amide bond formation has seen notable advancements through NHC catalysis. Given the wide application of amides in pharmaceuticals, agrochemicals, and materials science, several NHC‐based strategies have emerged for synthesizing amides from substrates such as aldehydes, alcohols, esters, and nitriles. This review highlights the sustainable and efficient nature of NHC‐catalyzed amide bond formation. Both metal–NHC complexes and metal‐free NHCs offer diverse catalytic pathways, with Ru–NHC systems proving especially effective in redox‐neutral amidations. NHCs promote reactions through mechanisms involving acyl azolium, hemiaminal, and Breslow intermediates, enabling high selectivity under mild conditions. Many of these methods align with green chemistry principles, featuring high atom economy and minimal waste generation. The versatility and tunability of NHC catalysts allow broad substrate compatibility, and recent innovations include metal‐free organocatalysis, continuous flow processes, and electrochemical amidation strategies. This review presents a comprehensive analysis of NHC‐catalyzed amide formation, summarizing key mechanisms, substrate scope, and catalyst design, emphasizing their dual role in metal‐based and organocatalytic sustainable amidation methods.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 17","pages":"Article e70036"},"PeriodicalIF":4.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135440","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}