{"title":"Continuous-flow carbonyl hydrogenation under subatmospheric to atmospheric hydrogen pressure enabled by robust heterogeneous Pt-Fe catalysts.","authors":"Hiroyuki Miyamura, Ryosuke Kajiyama, Shun-Ya Onozawa, Yoshihiro Kon, Shū Kobayashi","doi":"10.3762/bjoc.22.43","DOIUrl":"https://doi.org/10.3762/bjoc.22.43","url":null,"abstract":"<p><p>The reduction of carbonyl compounds, including ketones and aldehydes, to alcohols is a fundamental and important reaction in organic synthesis. One of the most ideal methods is catalytic hydrogenation, however, the hydrogenation of ketones generally requires harsh reaction conditions, such as high temperature and high pressure. We developed a bimetallic Pt-Fe nanoparticle catalyst immobilized on a composite support of dimethylpolysilane and alumina. Both ketones and aldehydes, including highly bulky and sterically hindered substrates, were smoothly hydrogenated using the newly developed catalysts under continuous-flow conditions at room temperature and under subatmospheric to atmospheric hydrogen pressure. High durability of the heterogeneous catalysts was confirmed by a long-term continuous-flow operation. Interestingly, both the combination of metal species and the metal ratio strongly influenced the catalytic performance.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"575-582"},"PeriodicalIF":2.1,"publicationDate":"2026-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13071934/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147687860","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":"Kinetic resolution of racemic planar-chiral vinylcymantrenes by molybdenum-catalyzed asymmetric metathesis dimerization.","authors":"Haruna Imazu, Hitoshi Izu, Yasuhiro Ohki, Masamichi Ogasawara","doi":"10.3762/bjoc.22.42","DOIUrl":"https://doi.org/10.3762/bjoc.22.42","url":null,"abstract":"<p><p>Highly diastereo- and enantioselective kinetic resolution (KR) of a series of racemic planar-chiral 1-R-2-vinylcymantrenes (<i>rac</i>-<b>1</b>; R = Br, Me, I) was realized by an asymmetric metathesis dimerization (AMD) reaction catalyzed by a chiral molybdenum-alkylidene precatalyst. The Mo/(<i>R</i>)-<b>L1</b> precatalyst promoted the AMD/KR reaction of <i>rac</i>-<b>1a</b> (R = Br) to give (<i>E</i>)-(<i>R</i>,<i>R</i>)-<b>2a</b> of 99% ee together with unreacted recovered (<i>S</i>)-<b>1a</b> of 45% ee at 37% conversion. The diastereoselectivity of this reaction was excellent with <i>chiral</i>-<b>2a</b>/<i>meso</i>-<b>2a</b> = 96:4 molar ratio, and the selectivity factor (<i>k</i> <sub>rel</sub>) was calculated to be 754 based on a second-order equation. In all the three substrates examined, the dimerized products, <i>chiral</i>-<b>2</b>, were obtained in >98% ee thanks to the outstanding enantioselectivity.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"568-574"},"PeriodicalIF":2.1,"publicationDate":"2026-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13058277/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147643690","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}
Catherine Gsell, Philipp Rebmann, Karina Opara, Christine Beuck, Peter Bayer, David Bier, Ingrid R Vetter, Thomas Schrader
{"title":"Molecular tweezer-peptide conjugates disrupt the protein-protein interaction between survivin and histone H3 essential in mitosis.","authors":"Catherine Gsell, Philipp Rebmann, Karina Opara, Christine Beuck, Peter Bayer, David Bier, Ingrid R Vetter, Thomas Schrader","doi":"10.3762/bjoc.22.41","DOIUrl":"https://doi.org/10.3762/bjoc.22.41","url":null,"abstract":"<p><p>Peptide-modified supramolecular tweezers, a promising new class of chemical tools, were designed and employed to inhibit the interaction of the BIR domain of human survivin, a member of the chromosomal passenger complex (CPC), with the phosphorylated histone H3 N-terminal peptide. Fluorescence polarization measurements revealed a nanomolar affinity of the BIR domain for the peptide-tweezer, depending on the presence of lysine residue 121, as proven by the K121A mutant of survivin. Two crystal structures of C-terminally truncated human survivin with the peptide-tweezer molecules demonstrated that the peptide moiety binds the BIR domain as expected from the well-known published crystal structures of survivin with various peptides, but the tweezer itself, surprisingly, was bound to a putative Ca<sup>2+</sup> ion and the side chain of Pro26, corresponding to a previously unknown binding mode. Guided by the accessibility of survivin's lysine residues in the CPC, a number of new promising peptide tweezers was synthesized, able to connect both binding sites on the protein.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"557-567"},"PeriodicalIF":2.1,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13040270/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147608090","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":"Experimental and DFT studies on the regioselective methanolysis of 5-azido-9-oxabicyclo[6.1.0]nonan-4-yl 4-nitrobenzoate isomers.","authors":"İlknur Polat, Selçuk Eşsiz, Emine Salamci","doi":"10.3762/bjoc.22.40","DOIUrl":"https://doi.org/10.3762/bjoc.22.40","url":null,"abstract":"<p><p>The regioselective methanolysis of new azido-4-nitrobenzoate epoxycyclooctane isomers and the characterization of the resulting products are described herein. Firstly, treatment of key compound 8-azidocyclooct-4-en-1-ol with 4-nitrobenzoyl chloride followed by an epoxidation reaction and then methanolysis of the epoxide ring and acetylation resulted in the formation of two corresponding chloro-acetate isomers. The structure of one of the chloro-acetate isomers was determined via crystallographic analysis and the other by 1D and 2D NMR spectroscopy. DFT computations confirm the regioselectivity of the methanolysis process, highlighting its precision and efficiency.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"547-556"},"PeriodicalIF":2.1,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13040264/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147608099","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}
Horst Weber, Kim-Thao Tran-Cong, Bernhard Mayer, Guido J Reiss, Iryna S Konovalova, Marc S Appelhans, Kenneth R Wood, Claus M Passreiter
{"title":"Melifoliox B, a novel phloroglucin derivative isolated from <i>Melicope barbigera</i> (Rutaceae) and synthesis of new oxidation products from melifoliones A and B.","authors":"Horst Weber, Kim-Thao Tran-Cong, Bernhard Mayer, Guido J Reiss, Iryna S Konovalova, Marc S Appelhans, Kenneth R Wood, Claus M Passreiter","doi":"10.3762/bjoc.22.39","DOIUrl":"https://doi.org/10.3762/bjoc.22.39","url":null,"abstract":"<p><p>In addition to new acetophenones and 2<i>H</i>-chromenes, the dichlormethane extract from leaves of <i>Melicope barbigera</i> A. Gray (Rutaceae) afforded a mixture of the isomeric melifoliones A (<b>1</b>) and B (<b>2</b>) as well as an oxidation product of <b>2</b>, whose structure was elucidated as the <i>para</i>-quinol <b>4</b>. For an independent synthesis of <b>4</b> and its possible isomer <b>3</b>, the required compounds <b>1</b> and <b>2</b> were synthesized as a mixture of the isomers starting from chromene <b>5</b>, briefly heated in a closed microwave apparatus with catalytic amounts of acetic acid. Forced heating of <b>5</b> in acetic acid or use of stronger acids lead to the benzoxocin derivatives <b>6</b> and <b>7</b>. Oxidation of melifoliones <b>1</b> and <b>2</b> under a great variety of oxidants and conditions failed to give <b>3</b> and <b>4</b>. Iodine-containing oxidants yielded the products <b>8</b>, <b>9</b>, and <b>10</b>. Combined oxidation with hydrogen peroxide and ferricyanide in alkaline solution resulted in an unexpected contraction of the acetyl phenol to a furanone ring, forming the derivatives <b>11</b> and <b>12</b>, whose structures were confirmed by X-ray analysis. A hypothetical mechanism for the oxidative ring contraction is proposed. <b>11</b> and <b>12</b> are the first representatives of new heterocyclic ring systems that have not previously been described in the literature.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"535-546"},"PeriodicalIF":2.1,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13040265/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147608102","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}
Julian Felix Maria Hebborn, Ben Eric Merten, Thomas Paululat, Heiko Ihmels
{"title":"Get a better glimpse on sequential photoreactions of trisnorbornadienes with <sup>19</sup>F NMR spectroscopy.","authors":"Julian Felix Maria Hebborn, Ben Eric Merten, Thomas Paululat, Heiko Ihmels","doi":"10.3762/bjoc.22.38","DOIUrl":"https://doi.org/10.3762/bjoc.22.38","url":null,"abstract":"<p><p>It is shown exemplarily with a trifluorinated trisnorbornadienylbenzene that <sup>19</sup>F NMR spectroscopy may be applied as a useful complementary method for the investigation of sequential photoreactions. The trisnorbornadiene core structure was used as it figures as promising scaffold for molecular solar thermal (MOST) energy storage. The target compound was readily synthesized by a Suzuki-Miyaura coupling reaction and examined with respect to the key properties for MOST applications. Upon direct or photosensitized irradiation, the trisnorbornadiene was transformed stepwise and almost quantitatively into the corresponding trisquadricyclane. Even though the reaction can be monitored by photometry or by in situ <sup>1</sup>H NMR spectroscopy, unambiguous assignment of the distinct intermediate mono- and bisquadricyclanes was not possible because of signal overlap. In contrast, this shortcoming is circumvented with in situ <sup>19</sup>F NMR-spectroscopic analysis. Contrary to the <sup>1</sup>H NMR spectra, the <sup>19</sup>F NMR spectra show significantly fewer characteristic and sufficiently separated signals that allow the unambiguous identification of all photoproducts and, thus, their detection in the course of the photoreaction.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"527-534"},"PeriodicalIF":2.1,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13040267/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147608063","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":"Modern synthetic pathways towards eribulin and its subunits.","authors":"Sebastian Dominik Graf","doi":"10.3762/bjoc.22.37","DOIUrl":"10.3762/bjoc.22.37","url":null,"abstract":"<p><p>Eribulin is a synthetic analog of halichondrin B, a natural product derived from marine sponges, and has gained significant importance in oncology (as its commercial mesylate salt, Halaven) due to its unique mechanism of action as a microtubule dynamics inhibitor. It is primarily used in the treatment of metastatic breast cancer and liposarcoma, offering a new therapeutic option for patients with advanced disease. To meet the increasing clinical demand, the research on new synthetic approaches is rigorously ongoing. Recent procedures mainly focus on more efficient and scalable techniques for the assembly of the 4 key fragments of eribulin. But also new pathways for the total synthesis have emerged in the last decade. In this review the latest advancements towards the construction of eribulin are summarized.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"495-526"},"PeriodicalIF":2.1,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13033900/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147589526","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}
Sara Karnib, Rana Baydoun, Wissam Zaidan, Nancy AlHaddad, Omar El Samad, Bilal Nsouli, Francine Cazier-Dennin, Pierre-Edouard Danjou
{"title":"Synthesis and uranyl(VI) extraction performance of a calix[4]pyrrole-tetrahydroxamic acid receptor.","authors":"Sara Karnib, Rana Baydoun, Wissam Zaidan, Nancy AlHaddad, Omar El Samad, Bilal Nsouli, Francine Cazier-Dennin, Pierre-Edouard Danjou","doi":"10.3762/bjoc.22.36","DOIUrl":"10.3762/bjoc.22.36","url":null,"abstract":"<p><p>The contamination of water by uranium poses a serious threat to ecosystems and human health, creating a need for efficient and selective remediation strategies. Supramolecular materials, with their pre-organized structures, offer a promising route for uranium removal. Phenoxycalix[4]pyrroles (PCP) are well-known supramolecular scaffolds capable of selective metal binding, making them attractive candidates for designing uranium extractants. Here, we report the design and synthesis of PCP HA, a phenoxycalix[4]pyrrole scaffold functionalized with four hydroxamic acid (HA) groups, and evaluate its uranium(VI) extraction potential. PCP HA was synthesized from its ester precursor (PCP E) via hydroxyaminolysis using KOH, achieving a 95% yield. Its structure was confirmed by <sup>1</sup>H NMR, <sup>13</sup>C NMR, and HRMS. The uranium(VI) extraction efficiency of PCP HA was evaluated by solid-liquid extraction experiments, using uranyl acetate as the uranium source, with measurements performed by gamma spectroscopy. PCP HA demonstrated good performance, removing up to 95% of uranyl(VI) from aqueous solutions (1 mM) at acidic pH, likely due to the strong coordination provided by its hydroxamic acid groups. Further studies revealed that the extraction efficiency also depends on the ligand-to-metal molar ratio. These findings establish PCP HA as a promising supramolecular material for the removal of uranyl from aqueous media.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"486-494"},"PeriodicalIF":2.1,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13033896/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147589543","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}
Wiktoria A Pytel, John W R Schwabe, James T Hodgkinson
{"title":"Synthesis of a HDAC inhibitor-nanogold probe for cryo-EM visualization in class I HDAC co-repressor complexes.","authors":"Wiktoria A Pytel, John W R Schwabe, James T Hodgkinson","doi":"10.3762/bjoc.22.35","DOIUrl":"10.3762/bjoc.22.35","url":null,"abstract":"<p><p>Class I histone deacetylases (HDACs 1-3) serve as catalytic subunits within seven multiprotein co-repressor complexes, each of which has distinct functions in the cell. We report the synthesis of a HDAC inhibitor-nanogold probe, derived from the class I HDAC inhibitor CI-994, for cryo-electron microscopy (cryo-EM) visualization of the HDAC catalytic domain within class I HDAC co-repressor complexes. The nanogold probe retained HDAC inhibitory activity comparable to CI-994 against the HDAC1-LSD1-CoREST complex in vitro. In cryo-EM studies, 2D class averages revealed the bi-lobed architecture of the CoREST complex and partial localization of the gold nanoparticle probe to the CoREST complex. However, the probe was not observed in classes showing the side-view of the CoREST complex, limiting unambiguous identification and positioning of the HDAC catalytic domain within the CoREST complex.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"480-485"},"PeriodicalIF":2.1,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13033894/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147589579","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 stereoselective synthesis of distal biaxially chiral molecules.","authors":"Fanxing Zhou, Chen Zhang, Lingyu Sun, Yiyun Fang, Siming Zheng, Lina Hu, Mengyang Shen, Zhen Zhao, Wei Xu, Yunqiang Sun, Zi-Qiang Rong","doi":"10.3762/bjoc.22.34","DOIUrl":"10.3762/bjoc.22.34","url":null,"abstract":"<p><p>Molecules bearing 1,3-dual axial and more distal axial chiralities are widely applied in chiral ligands, natural products, and anticancer agents, with their unique spatial configurations endowing them with distinctive functions and values. Although significant progress has been made in the asymmetric synthesis of distal biaxial chirality, overcoming the challenges of steric complexity and dynamic stability to achieve efficient and general construction remains a critical issue. This review summarizes recent advances in the field of distal biaxial chirality, highlighting three major synthetic strategies: direct one-step construction of distal biaxial chirality, multistep sequential generation, and conversion from central to biaxial chirality, with the aim of providing new perspectives and methodologies for further development in this area.</p>","PeriodicalId":8756,"journal":{"name":"Beilstein Journal of Organic Chemistry","volume":"22 ","pages":"461-479"},"PeriodicalIF":2.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13033899/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147589500","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}