Jin-Xin Lan, Yu Shu, Yang Zhou, Liu-Yu Shen, Fei Meng, Wen-Chao Yang
{"title":"Transition-metal-free K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-promoted oxidative C-C triple bond cleavage and esterification leading to α-ketoesters.","authors":"Jin-Xin Lan, Yu Shu, Yang Zhou, Liu-Yu Shen, Fei Meng, Wen-Chao Yang","doi":"10.1039/d5ob00892a","DOIUrl":"https://doi.org/10.1039/d5ob00892a","url":null,"abstract":"<p><p>A sustainable method for converting alkynes into α-ketoesters is reported through K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>-promoted oxidative C-C triple bond cleavage and esterification. This approach avoids transition metal catalysis, photocatalysts, and pure oxygen conditions, making it both efficient and more convenient.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558557","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}
Mohit Dhiman, Joseph T Smith, Christopher A Hunter
{"title":"Supramolecular assembly properties of a mixed-sequence recognition-encoded melamine oligomer.","authors":"Mohit Dhiman, Joseph T Smith, Christopher A Hunter","doi":"10.1039/d5ob00769k","DOIUrl":"10.1039/d5ob00769k","url":null,"abstract":"<p><p>Recognition-encoded melamine oligomers (REMO) are composed of an alternating piperazine-triazine backbone and side-chains equipped with either a H-bond donor (phenol, D) or a H-bond acceptor (phosphine oxide, A). Complementary homo-oligomers form stable duplexes in organic solvents, due to intermolecular base-pairing interactions between the phenol and phosphine oxide side-chains. For mixed-sequence oligomers, the major pathway that competes with duplex formation is folding due to intramolecular base-pairing interactions. Automated solid phase synthesis was used to prepare the self-complementary REMO DADA, and this oligomer was used to investigate the competition between intermolecular and intramolecular H-bonding interactions. Isothermal titration calorimetry in chloroform showed that DADA forms a dimeric complex, but with reduced stability compared with the duplexes formed by shorter oligomers. The results indicate that a folded state with intramolecular interactions between the two terminal recognition units is significantly populated. The dimeric complex formed at higher concentrations could involve the interaction of two folded oligomers in a kissing stem-loops structure, or the oligomer could unfold to give the duplex with four intermolecular base-pairs. One end of the oligomer was equipped with an azide and the other with an alkyne, so that the dimeric complex could be covalently trapped using copper-catalysed azide-alkyne cycloaddition reactions. The major product was the macrocyclic duplex with small amounts of the macrocyclic single-strand, which shows that the DADA·DADA duplex dominates at millimolar concentrations. Understanding the propensity of the REMO architecture to fold will help guide the future design principles for synthesis of more complex functional assemblies.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558547","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}
Juan Zhao, Hui-Min Qian, You Zi, Shun-Jun Ji, Xiao-Ping Xu
{"title":"Mild and efficient construction of nitrogen-containing heterocycles from <i>ortho</i>-ethynylbenzaldehydes and anilines.","authors":"Juan Zhao, Hui-Min Qian, You Zi, Shun-Jun Ji, Xiao-Ping Xu","doi":"10.1039/d5ob00634a","DOIUrl":"https://doi.org/10.1039/d5ob00634a","url":null,"abstract":"<p><p>A mild and transition-metal-free strategy for the synthesis of isoindolin-1-imines and isoquinolinium salts has been developed using <i>ortho</i>-ethynylbenzaldehydes and anilines. HFIP was employed as an effective promoter, facilitating nucleophilic addition and annulation to afford diverse isoindolin-1-imines in good yields. Alternatively, isoquinolinium salts were obtained by addition of ammonium iodide. Both reactions exhibited broad functional group tolerance and were successfully applied on gram scales as well as for further transformation, providing a practical strategy in pharmaceutical development and organic synthesis.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558546","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":"Ruthenium-catalysed isomerisation-methylenation of allyl alcohols with methanol: a one-pot synthesis of substituted pyridines.","authors":"Priyabrata Biswal, Sanu Siyad Pullarat, Shaikh Samser, Basava Punna Rao Aradhyula, Vadapalli Chandrasekhar, Krishnan Venkatasubbaiah","doi":"10.1039/d5ob00881f","DOIUrl":"https://doi.org/10.1039/d5ob00881f","url":null,"abstract":"<p><p>A simple bench-stable ruthenium complex facilitates the synthesis of tetra-substituted pyridines in one pot <i>via</i> isomerisation-methylenation of allyl alcohol using methanol as a C1 source. This methodology is applicable to a broad range of electronically diverse diaryl and monoaryl allyl alcohols, making it highly robust for synthesising substituted pyridines. Mechanistic investigations, including control experiments and isotope labelling studies, demonstrate the involvement of metal hydride species in the isomerisation-methylenation of allyl alcohol. Additionally, many of the tetra-substituted pyridines synthesised using this methodology exhibited good photophysical properties, illustrating its potential to generate interesting materials with applicability in organic electronics.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144551468","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":"Improvement of <i>N</i>-benzoylation catalysis driven by an amyloid-substrate complex.","authors":"Kai Yamamoto, Taka Sawazaki, Youhei Sohma","doi":"10.1039/d5ob00593k","DOIUrl":"https://doi.org/10.1039/d5ob00593k","url":null,"abstract":"<p><p>Nucleophilic reactions of amines are important chemical transformations, but the reactions are incompatible with acidic buffer conditions. Azo-stilbene is a motif that binds to amyloids formed by accumulation of β-sheet peptides. We previously reported that the amino group attached to azo-stilbene is activated by proximity to an amyloid catalyst, promoting nucleophilic reactions in acidic buffers. Here, we show that we could improve the <i>N</i>-benzoylation yield for what was previously a difficult substrate by (1) derivatizing an amyloid catalyst, (2) modulating the amyloid morphology with His, and (3) adding thioflavin-T as a reaction additive. These results are predicted to accelerate the application of the amine modification catalysis system driven by the amyloid-substrate complex and to advance research on functional molecules containing an azo-stilbene motif.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144537475","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":"Production of subtilosin A in <i>E. coli</i>: insights into the head-to-tail macrocyclization.","authors":"Yifei Jia, Yuanjun Han, Wenning Wang, Qi Zhang","doi":"10.1039/d4ob01816h","DOIUrl":"https://doi.org/10.1039/d4ob01816h","url":null,"abstract":"<p><p>Subtilosin A is the canonical member of the sactipeptide family with significant antimicrobial properties. In this study, we successfully produced subtilosin A in <i>Escherichia coli</i> by coexpressing the precursor peptide SboA with the radical SAM enzyme AlbA, and the metalloenzymes AlbE and AlbF. Our findings demonstrate that both AlbE and AlbF are essential for the head-to-tail macrocyclization of subtilosin A. We also identified an open-chain analog of subtilosin A, subtilosin A<sub>OC</sub>, which retains the thioether crosslinks but lacks the macrocyclic structure. Subtilosin A<sub>OC</sub> is likely a biosynthetic intermediate of subtilosin A, which exhibits observable but significantly decreased antibacterial activity compared to subtilosin A. These results provide valuable insights into the biosynthesis of subtilosin A and pave the way for future research on the sactipeptide family of natural products.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144537478","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}
Karolina Wojtczak, Emilie Gillon, Diana Bura, Karen Richmond, Megan Joyce, Emma Caraher, Keela Kessie, Trinidad Velasco-Torrijos, Cristina Trujillo, Anne Imberty, Kevin Kavanagh, Gordon Cooke, Joseph P Byrne
{"title":"Antiadhesive glycoconjugate metal complexes targeting pathogens <i>Pseudomonas aeruginosa</i> and <i>Candida albicans</i>.","authors":"Karolina Wojtczak, Emilie Gillon, Diana Bura, Karen Richmond, Megan Joyce, Emma Caraher, Keela Kessie, Trinidad Velasco-Torrijos, Cristina Trujillo, Anne Imberty, Kevin Kavanagh, Gordon Cooke, Joseph P Byrne","doi":"10.1039/d5ob00970g","DOIUrl":"https://doi.org/10.1039/d5ob00970g","url":null,"abstract":"<p><p>Glycoconjugates are known to interact with carbohydrate-binding proteins involved in adhesion by pathogens, and offer opportunities to design antimicrobial agents. Metal complexes with Eu(III), Ni(II) and Zn(II) were prepared from glycoconjugate ligand 1Gal, which binds to <i>P. aeruginosa</i>'s lectin LecA (<i>K</i><sub>d</sub> 9.6 ± 0.7 μM). <i>In vitro</i> anti-adhesive activity of these compounds was evaluated for both <i>P. aeruginosa</i> and <i>C. albicans</i>. Choice of metal ion played a crucial role in modulating anti-adhesive activity, with Eu(III) complexes most effective: [Eu·(1Gal)(H<sub>2</sub>O)<sub>6</sub>](CF<sub>3</sub>SO<sub>3</sub>)<sub>3</sub> inhibits 60% biofilm formation by <i>P. aeruginosa</i> and [Eu·(1Gal)<sub>3</sub>](CF<sub>3</sub>SO<sub>3</sub>)<sub>3</sub> inhibits 62% of <i>C. albicans</i> adhesion to buccal epithelial cells (both at 0.1 mM). The results presented demonstrate the potential for metal coordination to significantly enhance biological activity of glycoconjugates, surpassing the effect of the ligand's modest lectin-binding affinity alone.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144537471","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}
Yongyue Luo, Wenyan Tian, Yang Zhou, Chuangchuang He, Xuebing Ma
{"title":"Efficient homogeneous-like enantioselective catalysis of a bulky chiral catalyst: covalent immobilization of chiral spirocyclic phosphoric acid onto polystyrene brushes grafted on SiO<sub>2</sub> nanospheres.","authors":"Yongyue Luo, Wenyan Tian, Yang Zhou, Chuangchuang He, Xuebing Ma","doi":"10.1039/d5ob00641d","DOIUrl":"https://doi.org/10.1039/d5ob00641d","url":null,"abstract":"<p><p>To solve the mass transfer limitation and multi-step immobilization of bulky chiral phosphoric acids in heterogeneous asymmetric catalysis, this paper develops a direct immobilization of (<i>R</i>)-6,6'-di(9-anthryl)spirobiindane phosphoric acid ((<i>R</i>)-AnSPA) <i>via</i> Friedel-Crafts alkylation onto SiO<sub>2</sub>-grafted poly(<i>p</i>-vinylbenzyl chloride) (PVBC) brushes (PVBC@SiO<sub>2</sub>) and hollow mesoporous PVBC nanospheres (HMPNs), affording supported organocatalysts (AnSPA#PVBC@SiO<sub>2</sub> and AnSPA@HMPNs), respectively. Owing to the good dispersibility of PVBC brushes in organic solvents, the PVBC brush-anchored (<i>R</i>)-AnSPA with an open-ended structure enables the enantioselective desymmetrization of oxetanes with mercaptobenzothiazoles to proceed in a homogeneous-like manner, leading to the improved mass transfer of reactants due to alleviative steric hindrance. Compared to the homogeneous (<i>R</i>)-AnSPA, the PVBC brush-anchored (<i>R</i>)-AnSPA shows decrements in yield and enantioselectivity below 2%. However, the HMPN-anchored (<i>R</i>)-AnSPA shows larger decrements in yields (3-6%) and enantioselectivities (3-7% ee). Furthermore, AnSPA#PVBC@SiO<sub>2</sub> exhibits good reusability in enantioselective desymmetrization with no significant decreases in yield and enantioselectivity. Particularly, the deactivated AnSPA#PVBC@SiO<sub>2</sub>, caused by the hydrolysis of phosphate ester in (<i>R</i>)-AnSPA, can be easily renovated to its fresh state by dealing with POCl<sub>3</sub>. Overall, the direct immobilization of (<i>R</i>)-AnSPA onto PVBC brushes and renovation of deactivated (<i>R</i>)-AnSPA provide an effective strategy for achieving high sustainability of expensive chiral spirocyclic phosphoric acids in large-scale synthesis.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144537474","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":"One-pot synthesis of <i>trans</i>-2,3-diaminoindolines through 2,3-diamination of electrophilic indolines.","authors":"Yuito Kobori, Keisuke Tokushige, Takumi Abe","doi":"10.1039/d5ob00877h","DOIUrl":"https://doi.org/10.1039/d5ob00877h","url":null,"abstract":"<p><p>Despite recent advances in the synthesis of 2,3-diaminoindole derivatives, construction of 2,3-diaminoindolines, whose two amine moieties on each molecule differ from one another has yet to be achieved. In this work, we developed a concise one-pot protocol for differentiated diamination involving reacting a C2,C3-electrophilic indole reagent with amines to access a variety of previously inaccessible 2,3-diaminoindolines. Furthermore, the synthetic utility of this protocol was demonstrated by a successful gram-scale reaction and further transformation of the 2,3-diaminoindolines.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144537477","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}
Min Yang, Xuanfeng Li, Tingxi Lai, Jian Xiao, Minghui Xu, Bin Chen, Hai-Liang Ni, Bi-Qin Wang, Ping Hu, Peng Cao
{"title":"Ni-Catalyzed intramolecular cyclization of Baylis-Hillman adducts of 2-cyanoaniline towards 2,3-dihydroquinolin-4(1<i>H</i>)-ones.","authors":"Min Yang, Xuanfeng Li, Tingxi Lai, Jian Xiao, Minghui Xu, Bin Chen, Hai-Liang Ni, Bi-Qin Wang, Ping Hu, Peng Cao","doi":"10.1039/d5ob00778j","DOIUrl":"https://doi.org/10.1039/d5ob00778j","url":null,"abstract":"<p><p>A Ni-catalyzed reductive cyclization of Baylis-Hillman adducts of 2-cyanoaniline is presented. A novel class of quinolin-4-ones containing a quaternary carbon center were synthesized in moderate to good yields. With <sup>i</sup>Pr-PyBOX as a chiral ligand, the catalytic enantioselective cyclization gave a moderate yield and ee.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144537476","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}