Beilstein Journal of Organic Chemistry最新文献

{"title":"Substituent effects in <i>N</i>-acetylated phenylazopyrazole photoswitches.","authors":"Radek Tovtik, Dennis Marzin, Pia Weigel, Stefano Crespi, Nadja A Simeth","doi":"10.3762/bjoc.21.66","DOIUrl":"https://doi.org/10.3762/bjoc.21.66","url":null,"abstract":"<p><p>Phenylazopyrazole photoswitches proved to be valuable structural motifs for various applications ranging from materials science to medicine. Despite their potential, their structural diversity is still limited and a larger pool of substitution patterns remains to be systematically investigated. This is paramount as electronic effects play a crucial role in the behavior of photoswitches and a deeper understanding enables their straightforward development for specific applications. In this work, we synthesized novel <i>N</i>-acylpyrazole-based photoswitches and conducted a comparative study with 33 phenylazopyrazoles, comparing their photoswitching properties and the impact of electronic effects. Using UV-vis and NMR spectroscopy, we discovered that simple acylation of the pyrazole moiety leads to increased quantum yields of isomerization, long <i>Z</i>-isomer life-times, good spectral separation, and high photostability.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"830-838"},"PeriodicalIF":2.2,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12035873/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143973554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"4-(1-Methylamino)ethylidene-1,5-disubstituted pyrrolidine-2,3-diones: synthesis, anti-inflammatory effect and in silico approaches.","authors":"Nguyen Tran Nguyen, Vo Viet Dai, Luc Van Meervelt, Do Thi Thao, Nguyen Minh Thong","doi":"10.3762/bjoc.21.65","DOIUrl":"https://doi.org/10.3762/bjoc.21.65","url":null,"abstract":"<p><p>Pyrrolidine-2,3-diones are important intermediates in the synthesis of numerous nitrogen-containing heterocycles which possess a broad spectrum of biological and pharmacological activities. In this article, we report the synthesis of 4-(1-methylamino)ethylidene-1,5-disubstituted pyrrolidine-2,3-diones via a reversible transimination reaction between Schiff' base (C=N) linkage-containing pyrrolidine-2,3-dione derivatives and methylamine with yields of 80 to 92%. In addition to nuclear magnetic resonance spectroscopy, the structure of 4-(1-methylamino)ethylidene-1,5-diphenylpyrrolidine-2,3-dione (<b>5a</b>) was also verified through single-crystal X-ray diffraction. Furthermore, the synthesized molecules were evaluated for compliance with established drug-likeness rules (Lipinski, Veber, Ghose, Egan, and Muegge), as well as ADMET properties. All compounds satisfied these criteria, indicating favorable oral bioavailability. Molecular docking analysis showed that compounds <b>5a</b>-<b>e</b> act as ligands for inducible nitric oxide synthase (iNOS), especially with Cys200 and Ser242 via hydrogen bonds. In addition, van der Waals interactions also contribute to the stabilization of the ligand-iNOS complexes. In particular, 4-(1-methylamino)ethylidene-5-phenyl-1-(3-nitrophenyl)pyrrolidine-2,3-dione (<b>5e</b>) exhibited the strongest binding affinity (-9.51 kcal/mol) and demonstrated significant inhibitory activity against nitric oxide (NO) production, with an IC₅₀ value of 43.69 ± 5.26 µM. The presence of an electron-withdrawing group (-NO₂ group) on the benzene ring at the 1-position of the pyrrolidine-2,3-dione subunit in compound <b>5e</b> may be responsible for the observed high inhibition activity due to the enhancement and optimization of hydrogen bonding with Cys200. These results underscore the potential of 4-(1-methylamino)ethylidenepyrrolidine-2,3-diones, especially compound <b>5e</b>, as promising scaffolds for the development of anti-inflammatory agents targeting iNOS-related pathologies.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"817-829"},"PeriodicalIF":2.2,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12035876/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143975550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and photoinduced switching properties of C₇-heteroatom containing push-pull norbornadiene derivatives.","authors":"Daniel Krappmann, Andreas Hirsch","doi":"10.3762/bjoc.21.64","DOIUrl":"https://doi.org/10.3762/bjoc.21.64","url":null,"abstract":"<p><p>We report the synthesis and characterization of heteroatom-incorporated norbornadiene (NBD) derivatives. Push-pull substitution on the 2 and 3 position as well as introduction of oxygen or nitrogen at position 7 of the NBD scaffold have led to the development of a new family of photoswitches. We studied the potential conversion of norbornadiene to quadricyclane (QC) isomers. As main investigation tools, UV-vis and NMR spectroscopy were utilized. We determined significant spectral features of the formed NBD species, including λ_max and λ_onset values, all of which exhibit redshifts compared to their isocyclic counterparts. Additionally, the selected QC isomers were subjected to thermal and catalytic back-conversion studies.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"807-816"},"PeriodicalIF":2.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12035880/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143973511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbon-rich materials: from polyaromatic molecules to fullerenes and other carbon allotropes.","authors":"Hiroko Yamada, Yoko Yamakoshi","doi":"10.3762/bjoc.21.62","DOIUrl":"https://doi.org/10.3762/bjoc.21.62","url":null,"abstract":"","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"798-799"},"PeriodicalIF":2.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12018895/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143953126","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Regioselective formal hydrocyanation of allenes: synthesis of β,γ-unsaturated nitriles with α-all-carbon quaternary centers.","authors":"Seeun Lim, Teresa Kim, Yunmi Lee","doi":"10.3762/bjoc.21.63","DOIUrl":"https://doi.org/10.3762/bjoc.21.63","url":null,"abstract":"<p><p>This study introduces a highly selective hydrocyanation method based on copper-catalyzed hydroalumination of allenes with diisobutylaluminum hydride, followed by the regio- and stereoselective allylation with <i>p</i>-toluenesulfonyl cyanide. The proposed methodology is efficient for accessing acyclic β,γ-unsaturated nitriles with α-all-carbon quaternary centers and achieves yields up to 99% and excellent regio- and <i>E</i>-selectivity. The reaction proceeds under mild conditions and shows broad applicability to di- and trisubstituted allenes. Its practicality is demonstrated through the gram-scale synthesis and functional group transformations of amines, amides, and lactams, emphasizing its versatility and synthetic significance.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"800-806"},"PeriodicalIF":2.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12018896/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent advances in the electrochemical synthesis of organophosphorus compounds.","authors":"Babak Kaboudin, Milad Behroozi, Sepideh Sadighi, Fatemeh Asgharzadeh","doi":"10.3762/bjoc.21.61","DOIUrl":"https://doi.org/10.3762/bjoc.21.61","url":null,"abstract":"<p><p>In this review, we describe recent advances in electrochemical green methods for the synthesis of various organophosphorus compounds through the formation of phosphorus-carbon, phosphorus-nitrogen, phosphorus-oxygen, phosphorus-sulfur, and phosphorus-selenium bonds. The impact of different electrodes is also discussed in this matter. Graphite, platinum, RVC, and nickel electrodes have been used extensively for the electrochemical synthesis of organophosphorus compounds. The recent advances in the electrochemical synthesis of organophosphorus compounds have made this method a promising method for preparing various structures. This review is an introduction to encourage scientists to use electrosynthesis as a green, precise, and low-cost method to prepare phosphorous structures.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"770-797"},"PeriodicalIF":2.2,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12018900/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143967381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"New advances in asymmetric organocatalysis II.","authors":"Radovan Šebesta","doi":"10.3762/bjoc.21.60","DOIUrl":"https://doi.org/10.3762/bjoc.21.60","url":null,"abstract":"","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"766-769"},"PeriodicalIF":2.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12018904/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143975907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development and mechanistic studies of calcium-BINOL phosphate-catalyzed hydrocyanation of hydrazones.","authors":"Carola Tortora, Christian Andreas Fischer, Sascha Kohlbauer, Alexandru Zamfir, Gerd M Ballmann, Jürgen Pahl, Sjoerd Harder, Svetlana B Tsogoeva","doi":"10.3762/bjoc.21.59","DOIUrl":"https://doi.org/10.3762/bjoc.21.59","url":null,"abstract":"<p><p>Asymmetric hydrocyanation of hydrazones, catalyzed by a calcium-BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle for the enantioselective synthesis of α-hydrazinonitriles is proposed based on insights gained from DFT calculations. Trimethylsilyl cyanide (TMSCN) has been used as a sacrificial cyanide source. We found that isocyanide (rather than cyanide) is a preferred coordination to calcium during the catalytic cycle, while the active catalyst prefers a side-on coordination of cyanide. The configuration-determining step is a hydrocyanation via a calcium isocyanide complex, whereas the rate-limiting step is that which recovers the calcium catalyst and replaces the TMS-bound product from the catalyst. While our experimental data demonstrate enantioselectivity values as high as 89% under certain conditions, the overall enantioselectivity achieved with the calcium catalyst remains modest, mainly due to competing pathways for the <i>Z</i>- and <i>E</i>-hydrazone isomers leading to opposite enantiomers. The experimental results confirm these computational proposals.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"755-765"},"PeriodicalIF":2.2,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12018919/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143964662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Copper-catalyzed domino cyclization of anilines and cyclobutanone oxime: a scalable and versatile route to spirotetrahydroquinoline derivatives.","authors":"Qingqing Jiang, Xinyi Lei, Pan Gao, Yu Yuan","doi":"10.3762/bjoc.21.58","DOIUrl":"https://doi.org/10.3762/bjoc.21.58","url":null,"abstract":"<p><p>In this study, we report the copper-catalyzed synthesis of tetrahydroquinoline derivatives via a domino reaction of aniline with cyclobutanone oxime. This method demonstrates a selective approach for generating bioactive tetrahydroquinoline scaffolds, which have broad applications in pharmaceutical chemistry. The reaction conditions were optimized for the effective formation of tetrahydroquinoline derivatives with varying substituents, showing high yields under mild conditions. Mechanistic studies suggest a catalytic cycle involving nucleophilic attack by the aniline on the cyclobutanone oxime, followed by cyclization to form the desired product.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"749-754"},"PeriodicalIF":2.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11995718/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143973099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Orthogonal photoswitching of heterobivalent azobenzene glycoclusters: the effect of glycoligand orientation in bacterial adhesion.","authors":"Leon M Friedrich, Thisbe K Lindhorst","doi":"10.3762/bjoc.21.57","DOIUrl":"https://doi.org/10.3762/bjoc.21.57","url":null,"abstract":"<p><p>Carbohydrate recognition is fundamental to a plethora of cellular processes and hence the elucidation of the structural determinants of the recognition process is a prerequisite for understanding and manipulating carbohydrate-protein interactions, such as in the inhibition of carbohydrate-specific bacterial adhesion. For receptor binding, glycoligands have to be properly oriented in three-dimensional space and additionally, secondary interactions exerted by multivalent glycoligands have an effect on affinity. A recently introduced orthogonally photoswitchable heterobivalent azobenzene Glc/Man glycocluster was utilized to examine these aspects of carbohydrate recognition in a bacterial adhesion-inhibition assay. The measured results were systematically contextualized employing new reference compounds such as the respective homobivalent Man/Man glycocluster. An in-depth study comprising the analysis of the photochromic properties and the potential as inhibitors of bacterial adhesion of the synthetic glycophotoswitches in their different isomeric states led to new insights into the role of ligand orientation in carbohydrate recognition. The experimental results were underpinned by molecular modeling.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"736-748"},"PeriodicalIF":2.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11995721/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143975552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}