European Journal of Organic Chemistry最新文献

[5+1] Annulation of Aza-o-quinone Methides with Primary Amines: Construction of 3,4-Dihydroquinazolin-2(1H)-one Derivatives"

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-13 DOI: 10.1002/ejoc.202500267

Gang Wang, Hao-Bin Liu, Zhao-Lin He

引用次数: 0

Hydrogen Bond-Assisted Excited State Switching and Fluoride Responsive Behavior of Orthogonal Spiroborate Ester Derived from Naturally Occurring α-Mangostin

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-13 DOI: 10.1002/ejoc.202401411

Swathy Unnikrishnapillai Saraswathy, Lekshmi Chandranpillai Lalithabai, Sandip Giri, Safa Ayoob, Simimole Haleema, Anakuthil Anoop, Sumalekshmy Sarojiniamma

{"title":"Hydrogen Bond-Assisted Excited State Switching and Fluoride Responsive Behavior of Orthogonal Spiroborate Ester Derived from Naturally Occurring α-Mangostin","authors":"Swathy Unnikrishnapillai Saraswathy, Lekshmi Chandranpillai Lalithabai, Sandip Giri, Safa Ayoob, Simimole Haleema, Anakuthil Anoop, Sumalekshmy Sarojiniamma","doi":"10.1002/ejoc.202401411","DOIUrl":"https://doi.org/10.1002/ejoc.202401411","url":null,"abstract":"This study presents a sustainable and efficient method for synthesizing a spiroborate ester (MBO) from α-mangostin (MN), a natural xanthonoid isolated from the pericarp of mangosteen fruit. The synthetic process, structural characterization and photophysical properties of MBO are thoroughly discussed. MBO exhibits an absorption band at 370 nm, with a shoulder around 410-450 nm in non-polar solvents, which shifts to 424 nm in polar protic solvents. The compound displays green to blue emission, with intensity decreasing in polar protic environments. These spectral changes result from hydrogen bond-assisted excited state switching between n-π* and π-π* states, as confirmed by computational studies. MBO also shows excellent anion binding properties, functioning as a dual-channel probe for both colorimetric and turn-on fluorescence detection of fluoride ions. This approach not only adds value to the residual mangosteen pericarp by converting it into a fluorescent sensor but also offers a semisynthetic, environmentally benign alternative to conventional organic receptors for fluoride detection.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"87 2 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608553","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}

引用次数: 0

Regioelective Hydroformylation of an α,β-Unsaturated Ester: Spectroscopic Studies on Catalytic Species and the Influence of Ligands on Regioselectivity

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-13 DOI: 10.1002/ejoc.202401115

Hannah Bork, Thorsten Rösler, Markus Leutzsch, Niklas Wessel, Andreas Vorholt, Harald Gröger

{"title":"Regioelective Hydroformylation of an α,β-Unsaturated Ester: Spectroscopic Studies on Catalytic Species and the Influence of Ligands on Regioselectivity","authors":"Hannah Bork, Thorsten Rösler, Markus Leutzsch, Niklas Wessel, Andreas Vorholt, Harald Gröger","doi":"10.1002/ejoc.202401115","DOIUrl":"https://doi.org/10.1002/ejoc.202401115","url":null,"abstract":"Hydroformylation of α,β‑unsaturated esters is an atom-economical route towards aldehydes as precursors for pharmaceuticals. In this work, regioselective hydroformylation of an α,β‑unsaturated ester to the β‑aldehyde was initially re-evaluated using a commercial Rh catalyst sample named [HRh(PPh3)4] due to reported high selectivity for the β-aldehyde with this type of catalyst. However, while such high selectivity was achieved, subsequent investigation of this sample by high-pressure NMR and in situ IR spectroscopy under process conditions revealed a behavior like a phosphine-free system, indicating that the sample is decomposed and may be present as rhodium carbonyl clusters. This hypothesis has been supported by hydroformylation experiments with and without phosphine ligands. While a strong decrease in regioselectivity to the β‑aldehyde was observed in the presence of triphenylphosphine as added ligand, phosphine-free rhodium complexes led to high regioselectivities. In detail, the hydroformylation showed high regioselectivity (91%) and overall selectivity to the β-aldehyde (70–77%) with [Rh6(CO)16] as well as [Rh(acac)(CO)2] as ligand-free rhodium complexes. With further unmodified, phosphine-free rhodium compounds as catalysts, again high regioselectivities (90–93%) towards the β-aldehyde were obtained. Thus, our results indicate that non-modified triphenylphosphine-free Rh catalysts are efficient catalysts for regioselective hydroformylation of β-aryl-substituted α,β-unsaturated carboxylates to the β-aldehyde.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619058","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}

引用次数: 0

Zinc (II) Imidoyl azide, an unexpected stable intermediate in the synthesis of the N,N’-bis((1H-tetrazol-5-yl)methyl)nitramide (BTMNA) with new insensitive explosive properties.

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/ejoc.202500079

Lucas Blanck, Thibaud Alaime, Geneviève Eck, Julie Perouel, Rachid Baati

{"title":"Zinc (II) Imidoyl azide, an unexpected stable intermediate in the synthesis of the N,N’-bis((1H-tetrazol-5-yl)methyl)nitramide (BTMNA) with new insensitive explosive properties.","authors":"Lucas Blanck, Thibaud Alaime, Geneviève Eck, Julie Perouel, Rachid Baati","doi":"10.1002/ejoc.202500079","DOIUrl":"https://doi.org/10.1002/ejoc.202500079","url":null,"abstract":"Tetrazoles provide a perfect balance between insensitivity and explosive performances and several synthetic routes are available to generate such compounds in high yields. When studying the two-step synthesis of N,N’-bis((1H-tetrazol-5-yl)methyl)nitramide (BTMNA), suggested by Shreeve et al., an unexpected intermediate structure was observed. This stable intermediate in aqueous conditions, reacted with hydrochloric acid to generate the desired tetrazole heterocycle suggesting the existence of a scarce organozinc imidoyl azide compound, also coined “open tetrazole”. This unusually stable structure is exceptionally isolated as a solid. Furthermore, the possibility of zinc ions coordinating several organic imidoyl azide molecules at the same time, creates a sparse and unprecedented coordination polymer. This new polymeric intermediate is revealed in the synthesis of BTMNA when the starting material, the iminodiacetonitrile (IDA), reacts with sodium azide in water with the assistance of zinc chloride. The intermediate was characterized by Infrared spectroscopy (IR), Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TGA), and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). The observation of such unprecedented intermediates shows the mechanism complexity of the Demko-Sharpless [3+2] cycloaddition and broadens the understanding of the formation and potential use of organic zinc imidoyl azide coordination polymers as insensitive explosives.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"54 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600029","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}

引用次数: 0

Nonenzymatic Carboxylate Phosphorylation in Water

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/ejoc.202500179

Weiqiang Chen, Joris Zimmermann, Jonas Dechent, Joseph Moran

{"title":"Nonenzymatic Carboxylate Phosphorylation in Water","authors":"Weiqiang Chen, Joris Zimmermann, Jonas Dechent, Joseph Moran","doi":"10.1002/ejoc.202500179","DOIUrl":"https://doi.org/10.1002/ejoc.202500179","url":null,"abstract":"The core pathways of autotrophic microbial metabolism have been proposed to be fossils of self‐organized prebiotic chemistry. In recent years, numerous reactions within these pathways have been shown to occur nonenzymatically, supporting this hypothesis. However, the phosphorylation of carboxylic acids to the corresponding acyl phosphates, a recurring metabolic reaction, has notably yet to be demonstrated without enzymes. Here we show that carboxylate phosphorylation is promoted by diamidophosphate (DAP) and sodium nitrite in the presence of water, driven by the release of dinitrogen. The reaction occurs in minutes at 0─50 oC to convert carboxylic acids to acyl amidophosphate intermediates, which then undergo nitrite‐promoted hydrolysis to give the corresponding acyl phosphates. The partial overlap in scope with important metabolic carboxylates and the concentrated acidic conditions likely limit its direct applicability in metabolic origins of life scenarios. Nonetheless, the work represents a step forward in understanding nonenzymatic carboxylate phosphorylation and helps clarify how the transformation might eventually be rendered compatible with a protometabolism.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608161","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}

引用次数: 0

Synthesis of Functionalized Cyclooctynes as Building Blocks for Non‐covalent Surface‐Orthogonal Chemistry

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/ejoc.202500124

Ulrich Koert, Dominik Scharf, Clara M. Jaschke, Sergei Ivlev

引用次数: 0

Synthesis of Heteroatom‐Containing Organic Molecules via Intramolecular Cross‐Dehydrogenative Coupling

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/ejoc.202500014

Aanchal Batra, Manjot Kaur, Pushpinder Singh, Kamal Nain Singh

{"title":"Synthesis of Heteroatom‐Containing Organic Molecules via Intramolecular Cross‐Dehydrogenative Coupling","authors":"Aanchal Batra, Manjot Kaur, Pushpinder Singh, Kamal Nain Singh","doi":"10.1002/ejoc.202500014","DOIUrl":"https://doi.org/10.1002/ejoc.202500014","url":null,"abstract":"Heterocyclic compounds or heterocycles constitute the most prominent class of organic chemistry. The extensive functional utility of these compounds in pharmaceuticals and material science has led to increased research interest in this area. Since heteroatom containing molecules hold a pivotal position in both chemistry and biology, a number of methodologies have already been known for their synthesis. However, advancement in the synthetic methodology for their construction under mild reaction conditions is highly important. In the current scenario of research, intramolecular cross‐dehydrogenative coupling has emerged as a promising strategy in the synthesis of complex organic molecules from simpler ones via direct C‐H functionalization. This one‐pot atom‐economic protocol can construct fused heterocycles that are both pharmaceutically and medicinally important. The present review focuses on transition‐metal free synthesis of heteroatom containing organic molecules intramolecularly through carbon‐carbon (C‐C) and carbon‐heteroatom (C‐X) bond formation reactions reported over past one decade.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608160","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}

引用次数: 0

Synthesis and Reaction Mechanisms for the Construction of Pyrrolo[1,2-a]quinoxalines and Pyrrolo[1,2-a]quinoxalin-4(5H)-ones

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/ejoc.202500143

Jiang Nan, Lei Yao

{"title":"Synthesis and Reaction Mechanisms for the Construction of Pyrrolo[1,2-a]quinoxalines and Pyrrolo[1,2-a]quinoxalin-4(5H)-ones","authors":"Jiang Nan, Lei Yao","doi":"10.1002/ejoc.202500143","DOIUrl":"https://doi.org/10.1002/ejoc.202500143","url":null,"abstract":"Pyrrolo[1,2-a]quinoxalines and pyrrolo[1,2-a]quinoxalin-4(5H)-ones are recognized as important tricyclic scaffolds due to their diverse pharmacological activities, including anticancer, anti-fungi, anti-tuberculosis, and antimalarial, as well as their roles as 5-HT3 receptor agonists and kinase inhibitors targeting CK2 and AKT, and others. Developing efficient and reliable synthetic approaches to access these compounds remains an attractive goal in contemporary medicinal chemistry and drug discovery. This review highlights recent advances in the synthesis of pyrrolo[1,2-a]quinoxalines and pyrrolo[1,2-a]quinoxalin-4(5H)-ones, particularly focusing on strategies that maintain the A and C-rings while constructing the B-ring through the formation of a-, b-, and c-bonds. The information collected describes the two key components of the synthesis process 1-(2-substitued-phenyl)-1H-pyrrole and aldehyde or its surrogate.\u0000This review also briefly summarizes the reaction mechanisms for the formation of tricyclic skeletons to determine the key factors governing the issues of productivity and regioselectivity. Through analysis of the advantages and disadvantages of existing synthetic methods, we predict that A-ring formation strategy-based pyrrolo[1,2-a]quinoxaline reactions will be developed in the future. We hope that this review will motivate the search for novel strategies to synthesize pyrrolo[1,2-a]quinoxalines and pyrrolo[1,2-a]quinoxalin-4(5H)-ones, accessing tricyclic skeletons that may have potential applications in medicinal chemistry, materials science, and many branches of chemistry.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600030","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}

引用次数: 0

Transformation of Anilines to 1-Azaspiro[4.5]decanes via Dearomatization and Palladium-Catalyzed aza-[3+2] Cycloaddition with Vinylcyclopropanes

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/ejoc.202500175

Tingxuan Xu, Jinhao Hu, Qiuqin He, Renhua Fan

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One-Pot, Three-Component Borrowing Hydrogen/Cyclization Synthesis of Benzimidazoles

IF 2.8 3区化学

European Journal of Organic Chemistry Pub Date : 2025-03-12 DOI: 10.1002/ejoc.202401441

Feng Xu, Hui Yu, Lilong Zhang

引用次数: 0