Beilstein Journal of Organic Chemistry最新文献

{"title":"Emerging trends in the optimization of organic synthesis through high-throughput tools and machine learning.","authors":"Pablo Quijano Velasco, Kedar Hippalgaonkar, Balamurugan Ramalingam","doi":"10.3762/bjoc.21.3","DOIUrl":"10.3762/bjoc.21.3","url":null,"abstract":"<p><p>The discovery of the optimal conditions for chemical reactions is a labor-intensive, time-consuming task that requires exploring a high-dimensional parametric space. Historically, the optimization of chemical reactions has been performed by manual experimentation guided by human intuition and through the design of experiments where reaction variables are modified one at a time to find the optimal conditions for a specific reaction outcome. Recently, a paradigm change in chemical reaction optimization has been enabled by advances in lab automation and the introduction of machine learning algorithms. Therein, multiple reaction variables can be synchronously optimized to obtain the optimal reaction conditions, requiring a shorter experimentation time and minimal human intervention. Herein, we review the currently used state-of-the-art high-throughput automated chemical reaction platforms and machine learning algorithms that drive the optimization of chemical reactions, highlighting the limitations and future opportunities of this new field of research.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"10-38"},"PeriodicalIF":2.2,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11730176/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142982573","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":"Chemical glycobiology.","authors":"Elisa Fadda, Rachel Hevey, Benjamin Schumann, Ulrika Westerlind","doi":"10.3762/bjoc.21.2","DOIUrl":"https://doi.org/10.3762/bjoc.21.2","url":null,"abstract":"","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"8-9"},"PeriodicalIF":2.2,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11702292/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142943556","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, structure and π-expansion of tris(4,5-dehydro-2,3:6,7-dibenzotropone).","authors":"Yongming Xiong, Xue Lin Ma, Shilong Su, Qian Miao","doi":"10.3762/bjoc.21.1","DOIUrl":"https://doi.org/10.3762/bjoc.21.1","url":null,"abstract":"<p><p>The polycyclic skeleton of tris(4,5-dehydro-2,3:6,7-dibenzotropone) is a key structural fragment in carbon schwarzites, a theoretical form of negatively curved carbon allotrope. This report presents a new synthesis of this compound using a Ni-mediated Yamamoto coupling reaction and structural analysis of it with X-ray crystallography. Interestingly, it is observed that tris(4,5-dehydro-2,3:6,7-dibenzotropone) crystallized from its solution in hexane resulting in colorless and yellow crystal polymorphs, where it adopts conformations of approximate <i>C</i> <i>_s</i> and <i>C</i> ₂ symmetry, respectively. Furthermore, expanding its π-skeleton through the Barton-Kellogg and Scholl reactions led to the successful synthesis of a curved polycyclic arene containing three heptagons and two pentagons.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"21 ","pages":"1-7"},"PeriodicalIF":2.2,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11702293/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142943557","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 of acenaphthylene-fused heteroarenes and polyoxygenated benzo[<i>j</i>]fluoranthenes via a Pd-catalyzed Suzuki-Miyaura/C-H arylation cascade.","authors":"Merve Yence, Dilgam Ahmadli, Damla Surmeli, Umut Mert Karacaoğlu, Sujit Pal, Yunus Emre Türkmen","doi":"10.3762/bjoc.20.273","DOIUrl":"10.3762/bjoc.20.273","url":null,"abstract":"<p><p>Acenaphthylene-fused heteroarenes with a variety of five- and six-membered heterocycles such as thiophene, furan, benzofuran, pyrazole, pyridine and pyrimidine were synthesized via an efficient Pd-catalyzed reaction cascade in good to high yields (45-90%). This cascade involves an initial Suzuki-Miyaura cross-coupling reaction between 1,8-dihalonaphthalenes and heteroarylboronic acids or esters, followed by an intramolecular C-H arylation under the same conditions to yield the final heterocyclic fluoranthene analogues. The method was further employed to access polyoxygenated benzo[<i>j</i>]fluoranthenes, which are all structurally relevant to benzo[<i>j</i>]fluoranthene-based fungal natural products. The effectiveness of our strategy was demonstrated via a concise, four-step synthesis of the tetramethoxybenzo[<i>j</i>]fluoranthene derivative <b>18</b>, which represents a formal total synthesis of the fungal natural product bulgarein.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"20 ","pages":"3290-3298"},"PeriodicalIF":2.2,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11693970/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142920538","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":"Reactivity of hypervalent iodine(III) reagents bearing a benzylamine with sulfenate salts.","authors":"Beatriz Dedeiras, Catarina S Caldeira, José C Cunha, Clara S B Gomes, M Manuel B Marques","doi":"10.3762/bjoc.20.272","DOIUrl":"10.3762/bjoc.20.272","url":null,"abstract":"<p><p>The reactivity of our recently disclosed hypervalent iodine reagents (HIRs) bearing a benzylamine with in situ-generated sulfenate salts was investigated. Under the studied conditions sulfonamides have been obtained in up to 52% yield. This reaction has been extended to a variety of HIRs and sulfenate salts to explore the different reactivity of these new reagents. A plausible mechanism is proposed, suggesting a possible radical pathway.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"20 ","pages":"3281-3289"},"PeriodicalIF":2.2,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11665445/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142881027","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":"Giese-type alkylation of dehydroalanine derivatives via silane-mediated alkyl bromide activation.","authors":"Perry van der Heide, Michele Retini, Fabiola Fanini, Giovanni Piersanti, Francesco Secci, Daniele Mazzarella, Timothy Noël, Alberto Luridiana","doi":"10.3762/bjoc.20.271","DOIUrl":"10.3762/bjoc.20.271","url":null,"abstract":"<p><p>The rising popularity of bioconjugate therapeutics has led to growing interest in late-stage functionalization (LSF) of peptide scaffolds. α,β-Unsaturated amino acids like dehydroalanine (Dha) derivatives have emerged as particularly useful structures, as the electron-deficient olefin moiety can engage in late-stage functionalization reactions, like a Giese-type reaction. Cheap and widely available building blocks like organohalides can be converted into alkyl radicals by means of photoinduced silane-mediated halogen-atom transfer (XAT) to offer a mild and straightforward methodology of alkylation. In this research, we present a metal-free strategy for the photochemical alkylation of dehydroalanine derivatives. Upon abstraction of a hydride from tris(trimethylsilyl)silane (TTMS) by an excited benzophenone derivative, the formed silane radical can undergo a XAT with an alkyl bromide to generate an alkyl radical. Consequently, the alkyl radical undergoes a Giese-type reaction with the Dha derivative, forming a new C(sp³)-C(sp³) bond. The reaction can be performed in a phosphate-buffered saline (PBS) solution and shows post-functionalization prospects through pathways involving classical peptide chemistry.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"20 ","pages":"3274-3280"},"PeriodicalIF":2.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11665442/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142881025","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":"Efficient synthesis of fluorinated triphenylenes with enhanced arene-perfluoroarene interactions in columnar mesophases.","authors":"Yang Chen, Jiao He, Hang Lin, Hai-Feng Wang, Ping Hu, Bi-Qin Wang, Ke-Qing Zhao, Bertrand Donnio","doi":"10.3762/bjoc.20.270","DOIUrl":"10.3762/bjoc.20.270","url":null,"abstract":"<p><p>The high potential of non-covalent arene-fluoroarene intermolecular interactions in the design of liquid crystals lies in their ability to strongly promote self-assembly, improve the order and stability of the supramolecular mesophases, and enable tuneability of the optical and electronic properties, which can potentially be exploited for advanced applications in display technologies, photonic devices, sensors, and organic electronics. We recently successfully reported the straightforward synthesis of several mesogens containing four lateral aliphatic chains and derived from the classical triphenylene core self-assembling in columnar mesophases based on this paradigm. These mesogenic compounds were simply obtained in good yields by the nucleophilic substitution (S_NFAr) of various types of commercially available fluoroarenes with the electrophilic organolithium derivatives 2,2'-dilithio-4,4',5,5'-tetraalkoxy-1,1'-biphenyl (2Li-<b>BP</b> <i>n</i>). In a continuation of this study, aiming at testing the limits of the reaction and providing a large diversity of structures, a structurally related series of compounds is reported here, namely 1,2,4-trifluoro-6,7,10,11-tetraalkoxy-3-(perfluorophenyl)triphenylenes (<b>F</b> <i>n</i>). They were obtained by reacting the above mentioned 2,2'-dilithiobiphenyl derivatives with decafluorobiphenyl, C₆F₅-C₆F₅. These compounds differ from the previously reported series, 1,2,4-trifluoro-6,7,10,11-tetraalkoxy-3-aryltriphenylenes (<b>PH</b> <i>n</i>), solely by the substitution of the terminal phenyl ring with a pentafluorophenyl ring. Thus, as expected, they display a Col_hex mesophase over large temperature ranges, with only small differences in the mesophase stability and transition temperatures. Furthermore, the presence of the terminal fluorophenyl group enables a subsequent second annulation, yielding a new series of extended polyaromatic mesomorphic compounds, i.e., 1,1',3,3',4,4'-hexafluoro-6,6',7,7',10,10',11,11'-octaalkoxy-2,2'-bitriphenylene (<b>G</b> <i>nm</i>) which were found to display a Col_rec mesophase. The specific nucleophilic substitution patterns of the <b>F</b> <i>n</i> derivatives and the antiparallel stacking mode into columnar structures stabilized by arene-perfluoroarene intermolecular interactions were confirmed by the single-crystal structure of the alkoxy-free side chain analog, i.e., 1,2,4-trifluoro-3-(perfluorophenyl)triphenylene (<b>F</b>). UV-vis absorption and fluorescence emission spectroscopies reveal green photoluminescence with fluorescence quantum yields of up to 33% for the <b>F</b> <i>n</i> derivatives. The <i>J</i>-aggregation for the inner fluorine-substituted dimers <b>G</b> <i>nm</i> is energetically and stereoelectronically more favorable and <b>G</b>66 exhibits thin-film fluorescence with a large red-shift of the emission peak.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"20 ","pages":"3263-3273"},"PeriodicalIF":2.2,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11665444/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880921","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":"Intramolecular C-H arylation of pyridine derivatives with a palladium catalyst for the synthesis of multiply fused heteroaromatic compounds.","authors":"Yuki Nakanishi, Shoichi Sugita, Kentaro Okano, Atsunori Mori","doi":"10.3762/bjoc.20.269","DOIUrl":"10.3762/bjoc.20.269","url":null,"abstract":"<p><p>The C-H arylation of 2-quinolinecarboxyamide bearing a C-Br bond at the <i>N</i>-aryl moiety is carried out with a palladium catalyst. The reaction proceeds at the C-H bond on the pyridine ring adjacent to the amide group in the presence of 10 mol % Pd(OAc)₂ at 110 °C to afford the cyclized product in 42% yield. The yield is improved to 94% when the reaction is performed with PPh₃ as a ligand of palladium. The reaction is examined with amides derived from unsubstituted picoline, 6-methylpicoline, and 2,6-pyridinedicarboxylic acid in a similar manner to afford the cyclized products in 70%, 77%, and 87% yield, respectively. The related reaction is also carried out with amides of non-pyridine derivatives terephthal- and benzamides to afford multiply fused heterocyclic compounds in 81% and 89% yields, respectively.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"20 ","pages":"3256-3262"},"PeriodicalIF":2.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11650519/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845667","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":"Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines.","authors":"Sergio Torres-Oya, Mercedes Zurro","doi":"10.3762/bjoc.20.268","DOIUrl":"10.3762/bjoc.20.268","url":null,"abstract":"<p><p>Asymmetric cycloaddition is a straightforward strategy which enables the synthesis of structurally distinct cyclic derivatives which are difficult to access by other methodologies, using an efficient and atom-economical path from simple precursors. In recent years several asymmetric catalytic cyclization strategies have been accomplished for the construction of <i>N</i>-heterocycles using various catalytic systems such as chiral metal catalysts, chiral Lewis acids or chiral organocatalysts. This review presents an overview of the recent advances in enantioselective cyclization reactions of 1-azadienes catalyzed by non-covalent organocatalysts.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"20 ","pages":"3221-3255"},"PeriodicalIF":2.2,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11650568/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845668","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":"Discovery of ianthelliformisamines D-G from the sponge <i>Suberea ianthelliformis</i> and the total synthesis of ianthelliformisamine D.","authors":"Sasha Hayes, Yaoying Lu, Bernd H A Rehm, Rohan A Davis","doi":"10.3762/bjoc.20.266","DOIUrl":"10.3762/bjoc.20.266","url":null,"abstract":"<p><p>The marine sponge <i>Suberea ianthelliformis</i> was investigated for new chemistry after the recent discovery that polyamines ianthelliformisamines A-C (<b>1</b>-<b>3</b>) - originally sourced from this Australian sponge - act as <i>Pseudomonas aeruginosa</i> biofilm inhibitors and antibiotic enhancers. Large-scale extraction and isolation studies resulted in the discovery of four new and minor natural products, ianthelliformisamines D-G (<b>4</b>-<b>7</b>) and the known steroid, aplysterol (<b>8</b>). Compounds <b>4</b>-<b>7</b> were fully characterised following 1D/2D NMR, MS and UV data analyses. All compounds were assessed for their inhibition on planktonic growth of <i>P. aeruginosa</i> PAO1 in addition to their ability to inhibit the formation of biofilms. None of the tested natural products inhibited planktonic growth or biofilm formation of PAO1 when screened at 50 µM. Ianthelliformisamine D (<b>4</b>) contains a rare <i>N</i>-(3-aminopropyl)-2-pyrrolidone moiety only found in <30 natural products. Owing to the novelty of compound <b>4</b>, we undertook the first total synthesis of this natural product, which was achieved in three steps.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"20 ","pages":"3205-3214"},"PeriodicalIF":2.2,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11650616/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845546","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}