Anna Vaisman , Hosein Tafazolian , Diana Stoianova , Jonathan M. Goldberg , Kristina Goulinian , Angelino Doppiu , Adam M. Johns , Norberto Gabriel Lemcoff
{"title":"Latent Ruthenium Complexes Supported by Two N‐Heterocyclic Carbene Ligands: Synthesis and Catalytic Activity with Distinctive Activation","authors":"Anna Vaisman , Hosein Tafazolian , Diana Stoianova , Jonathan M. Goldberg , Kristina Goulinian , Angelino Doppiu , Adam M. Johns , Norberto Gabriel Lemcoff","doi":"10.1002/ejoc.202500284","DOIUrl":"10.1002/ejoc.202500284","url":null,"abstract":"<div><div>Novel bis(<em>N</em>‐heterocyclic carbene [NHC]) ruthenium complexes of the form (NHC<sup>1</sup>)(NHC<sup>2</sup>)Ru(=CRR')Cl<sub>2</sub> (where NHC represents <em>N</em>‐heterocyclic carbene ligands and CRR’ denotes Ph‐indenylidene or benzylidene moieties) are prepared from second‐ and third‐generation Grubbs catalysts. These complexes exhibit thermal latency in ring‐closing metathesis (RCM), cross‐metathesis (CM), and several ring‐opening metathesis polymerization (ROMP) reactions. Upon UV‐C (255 nm) irradiation, two complexes that contained benzylidene ligands prove to be highly effective for the ROMP of cyclooctadiene. The most active species incorporate IPr or SIPr as at least one NHC ligand, highlighting how bulky isopropyl substituents enhance NHC lability. Beyond their utility in UV‐C‐initiated ROMP, these complexes show promising activity for high‐temperature CM and RCM of alkenyl‐nitrile substrates.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 24","pages":"Article e202500284"},"PeriodicalIF":2.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677599","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xinru Li , Zhongnan Xu , Shenting Zhang , Wenzhu Yu , Shen Tan , Martin G. Banwell
{"title":"Total Syntheses of the Linearly‐Fused Prenylated Indole Alkaloids Asperversiamides H and M via Oxidative Rearrangement of the Putative Biosynthetic Precursor Dihydrocarneamide A","authors":"Xinru Li , Zhongnan Xu , Shenting Zhang , Wenzhu Yu , Shen Tan , Martin G. Banwell","doi":"10.1002/ejoc.202500277","DOIUrl":"10.1002/ejoc.202500277","url":null,"abstract":"<div><div>An improved synthesis of the alkaloid dihydrocarneamide A is reported and this has been subjected to a biomimetic‐type oxidative rearrangement using an oxaziridine and so affording the oxidole‐containing and prenylated indole alkaloids (PIAs) asperversiamides H and M. This work serves to confirm the structure assigned to the latter. Oxidation of dihydrocarneamide A using <em>m</em>‐chloroperbenzoic (<em>m</em>‐CPBA) affords an oxidative fragmentation product representing the linear isomer of the PIA amoenamide A and thus a potential “natural product in‐waiting”. Furthermore, oxaziridine‐mediated oxidation of the epimer of dihydrocarneamide A (and the enantiomer of the structure assigned to the natural product asperversiamide F) afforded a mixture of two hitherto unreported oxindoles. Given the manner in which these last two products have been formed it seems likely that these, too, are “natural products in‐waiting”. Certain cytotoxic and antimicrobial properties of key compounds are reported.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 24","pages":"Article e202500277"},"PeriodicalIF":2.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Mechanistic Insights into the [3+2] Cycloaddition Reaction of Azomethine Ylides with Methyl Vinyl Ketone in the Triplet Excited State: A Molecular Electron Density Theory Study","authors":"Luis R. Domingo , Patricia Pérez , Assem Barakat","doi":"10.1002/ejoc.202500241","DOIUrl":"10.1002/ejoc.202500241","url":null,"abstract":"<div><div>The [3+2] cycloaddition (32CA) reaction of an azomethine ylide with methyl vinyl ketone in the ground and first triplet excited states has been studied within the framework of molecular electron density theory. A density functional theory‐based reactivity analysis indicates that, while azomethine ylide behaves as a supernucleophile in both states, vinyl ketone acts as a strong electrophile. This 32CA reaction presents a very low activation energy both in the ground state, 3.40 kcal mol<sup>−1</sup>, and in the triplet state, 1.47 kcal mol<sup>−1</sup>, in the gas phase. While in the ground state, the 32CA reaction is entirely <em>ortho</em> regio and fully <em>endo</em> stereoselective, in the triplet state it is entirely <em>ortho</em> regioselective but only partially <em>endo</em> stereoselective. In the ground state, the reaction proceeds to form the spirooxindole after passing through the transition state structure, whereas in the triplet state, the reaction stops at a biradical intermediate, which requires an intersystem crossing to yield the final spirooxindole. Analysis of the kinetic parameters of the 32CA reaction in the two states in methanol indicates that in the triplet state, the reaction is only 589 times faster than in the ground state.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 24","pages":"Article e202500241"},"PeriodicalIF":2.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143946208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Oscar Javier Gamboa Marin , Nitish Verma , Maude Cloutier , Charles Gauthier
{"title":"Synthesis of Rhamnose‐Modified Lewis‐X‐Containing Saponins","authors":"Oscar Javier Gamboa Marin , Nitish Verma , Maude Cloutier , Charles Gauthier","doi":"10.1002/ejoc.202500285","DOIUrl":"10.1002/ejoc.202500285","url":null,"abstract":"<div><div>The synthesis of betulinic acid and echinocystic acid saponins featuring an unnatural analogue of the Lewis‐X trisaccharide, in which the <span>l</span>‐fucose residue is replaced by <span>l</span>‐rhamnose, is reported. These triterpenoid saponins are designed as negative controls for dendritic cell‐specific intercellular adhesion molecule‐3‐grabbing nonintegrin‐targeted antiviral and immunological studies. The target saponins are synthesized using both iterative and convergent strategies, requiring nine and six steps, respectively, for the longest linear sequence starting from allyl betulinate and allyl echinocystate. Glycosylation reactions are performed using trihalogenoacetimidate and thioglycoside donors, which provide excellent yields and complete control over stereoselectivity. This work establishes a robust foundation for the synthesis of lupane‐ and oleanane‐type triterpenoid saponins incorporating Lewis‐X trisaccharide analogues.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 24","pages":"Article e202500285"},"PeriodicalIF":2.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jay Hanssens , Diego Meneses , Jordy M. Saya , Romano V. A. Orru
{"title":"Terpenes and Terpenoids: How can we use them?","authors":"Jay Hanssens , Diego Meneses , Jordy M. Saya , Romano V. A. Orru","doi":"10.1002/ejoc.202401151","DOIUrl":"10.1002/ejoc.202401151","url":null,"abstract":"<div><div>As one of the twelve fundamental principles of green chemistry, the employed feedstocks in chemical processes received substantial attention over the past decades. These efforts can be attributed to Werpy's 2004 list of top‐value‐added chemicals from biomass. Conventional fossil‐based feedstocks are both depleting and environmentally damaging, leading to the transition towards renewable, bio‐based platform chemicals. Terpenes and terpenoids are a group of bio‐based compounds well known throughout the scientific community. Although their acquirement from natural feedstocks is well known, comprehensive overviews of their applications in synthetic chemistry remain limited. Herein, a full comprehensive overview of the reported chemistry with terpenes is provided, while specifically highlighting their reactivity. Fifteen of the most common and useful monoterpenes and terpenoids are discussed, followed by a list of the remaining known compounds belonging to this group. These fifteen compounds have been employed in a vast number of chemical transformations with different applications including: polymerizations, total syntheses, chiral reagents/auxiliaries, pharmaceuticals, and chemical conversion to other useful bio‐based chemicals. The presented chemistry in this work aims to provide chemists with a useful tool that should facilitate and stimulate the search for more sustainable, renewable, and environmentally friendly starting points for novel synthesis routes.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 24","pages":"Article e202401151"},"PeriodicalIF":2.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Manikanta Swami Pothana , Huang‐Chieh Lu , Bor‐Cherng Hong , Su‐Ying Chien
{"title":"Total Synthesis of Pegaharmine I Enabled by Visible‐Light Photocatalytic Nitrone Formation","authors":"Manikanta Swami Pothana , Huang‐Chieh Lu , Bor‐Cherng Hong , Su‐Ying Chien","doi":"10.1002/ejoc.202500245","DOIUrl":"10.1002/ejoc.202500245","url":null,"abstract":"<div><div>The first total synthesis of pegaharmine I is accomplished by a three‐step strategy featuring a visible‐light‐photocatalyzed nitrone formation reaction as the key step. The structure of this natural product is confirmed by crystallographic analysis. Water‐promoted photocatalysis, achieved by incorporating water into the reaction medium, has also been established.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 24","pages":"Article e202500245"},"PeriodicalIF":2.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Karthik Rajan Rajamanickam, Robin Prakash Sirvin Rajan, Nithin Pootheri, Chin-Fa Lee, Sunwoo Lee
{"title":"Front Cover: Recent Advances in Transition Metal-Free Strategies for the Transformation of Amides into Carbonyl Compounds (Eur. J. Org. Chem. 23/2025)","authors":"Karthik Rajan Rajamanickam, Robin Prakash Sirvin Rajan, Nithin Pootheri, Chin-Fa Lee, Sunwoo Lee","doi":"10.1002/ejoc.202582301","DOIUrl":"https://doi.org/10.1002/ejoc.202582301","url":null,"abstract":"<p><b>The Front Cover</b> illustrates the expanding universe of transition-metal-free amide bond transformations. At the center of the image, a stylized amide framework is surrounded by orbiting motifs that represent diverse carbonyl-based derivatives and reactive intermediates. This visual composition emphasizes the wide substrate scope and synthetic utility of amides, enabling the selective formation of C─N, C─C, C─O, C─H, and C─X bonds. The dynamic layout symbolizes the conceptual shift from traditional metal-catalyzed processes to sustainable and practical alternatives in modern organic synthesis. More information can be found in the Review by C.-F. Lee, S. Lee and co-workers (DOI: 10.1002/ejoc.202500210).\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 23","pages":""},"PeriodicalIF":2.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejoc.202582301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144367419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Introduction of Structural Diversity at the C2 Position of Unsaturated Iminosugars through Palladium‐Catalysed Cross‐Coupling Reactions","authors":"Yves Bleriot, angelique ferry, quentin joachim, delphine carry, mattéo di pasquale, jerome marrot, jacques uziel, nadege lubin-germain, Jerome desire, atsushi kato, suzuka yamamoto","doi":"10.1002/ejoc.202500502","DOIUrl":"https://doi.org/10.1002/ejoc.202500502","url":null,"abstract":"To vary the functionality of iminosugars at the C2 position, protected 2‐iodoiminoglycals in the D‐gluco, D‐galacto and D‐xylo series were efficiently synthesized from sugar lactams. Their mild palladium‐catalyzed aminocarbonylation, arylation and phosphonylation were successful and provided a range of C2‐functionalized iminoglycals in good yields. Two of these compounds were O‐deprotected to afford 1,2‐unsaturated iminosugars that proved to be modest inhibitors of glycosidases.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"640 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144370612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Rhodium(II)‐Catalyzed Oxo‐Amination of Aryl Cyclopropanes","authors":"Zhiying Fan , Nengde Liang , Yuanhua Wang","doi":"10.1002/ejoc.202500235","DOIUrl":"10.1002/ejoc.202500235","url":null,"abstract":"<div><div>A rhodium(II)‐catalyzed method is described for synthesizing β‐amino ketones from aryl cyclopropanes, utilizing water as an oxygen source and <em>N</em>‐fluorobis(benzenesulfonamide) as a commercially available nitrogen source. This approach offers good substrate tolerance under mild conditions, providing a novel and practical route for β‐amino ketone synthesis. Mechanistic studies reveal a sequential cascade pathway initiated by single‐electron transfer facilitated by the rhodium(II) catalyst, followed by hydrogen atom transfer and radical polar crossover steps. These insights underscore the potential of rhodium(II) in driving radical amination reactions, enhancing the synthesis of β‐amino ketones from simple precursors.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 23","pages":"Article e202500235"},"PeriodicalIF":2.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Narsimhaswamy Dubasi , Ravi Varala , Murali Mohan Achari Kamsali , Mohammed Mujahid Alam
{"title":"Visible Light‐Driven Multicomponent Reactions for the Synthesis of Diverse Heterocyclic Frameworks","authors":"Narsimhaswamy Dubasi , Ravi Varala , Murali Mohan Achari Kamsali , Mohammed Mujahid Alam","doi":"10.1002/ejoc.202500216","DOIUrl":"10.1002/ejoc.202500216","url":null,"abstract":"<div><div>The characteristics of visible light, including its sustainability, eco‐friendliness, and potential for renewable energy, have made visible light‐powered catalysis an intriguing research topic of great interest. In this case, photoredox catalysis uses a single‐electron transfer mechanism under mild reaction conditions to produce very reactive radical species with frequently unusual reactivities. This work is the most comprehensive review of photochemical methods for producing divergent heterocycles through multicomponent reactions, covering important developments since 2021. This review is structured according to the kind of synthesized heterocyclic scaffold. Additionally, different study findings’ scopes, limitations, and mechanistic studies are covered.</div></div>","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"28 23","pages":"Article e202500216"},"PeriodicalIF":2.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}