{"title":"The Two Janus Faces of CpRu-Based Deallylation Catalysts and Their Application for in Cellulo Prodrug Uncaging","authors":"Alain Baiyoumy, Robin Vinck, Thomas R. Ward","doi":"10.1002/hlca.202400053","DOIUrl":"10.1002/hlca.202400053","url":null,"abstract":"<p>In the past 18 years, metal-catalyzed deallylation has proven a useful tool for studying biological processes <i>in cellulo</i> and in the early development of innovative therapeutic catalytic strategies. This reaction is catalyzed by Ru-piano stool complexes and has been reported to be compatible with air, water, and thiol-containing compounds such as glutathione. However, little is known about the true influence of biological components on the outcome of this reaction. The results presented herein reveal that the co-solvent used in the reaction affects the complex's stability and activity in air, while the presence of glutathione contributes to minimizing the formation of <i>N-</i>allylated by-products. In addition, we studied the effect of air on the Ru-catalyzed deallylation. Importantly, we found that, in the presence of air, the complex is deactivated and oxidizes glutathione into its disulfide.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 7","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400053","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140572001","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}
Alain Trachsel, Sabine Leocata, Jean-Yves de Saint Laumer, Andreas Herrmann
{"title":"Controlled Release of Volatile Enones from Monomeric and Dimeric Thioether, Sulfoxide and Sulfone Profragrances","authors":"Alain Trachsel, Sabine Leocata, Jean-Yves de Saint Laumer, Andreas Herrmann","doi":"10.1002/hlca.202400046","DOIUrl":"10.1002/hlca.202400046","url":null,"abstract":"<p>Thioether (sulfide) profragrances are readily prepared by 1,4-addition of alkanethiols to enones (thia-<i>Michael</i> reaction). Under ambient conditions, they slowly release the parent enones, thus generating a long-lasting perfumery effect. The fragrance release of profragrances obtained by 1,4-addition of S, O and N nucleophiles to enones was compared on cotton and on a hard surface for monomeric and dimeric structures. To avoid the uncontrolled generation of volatile sulfur compounds from thioethers, we investigated the extent to which different side reactions occurred next to the expected formation of enones and alkanethiols. Headspace analyses on cotton showed that enones and aldehydes were the major reaction products, whereas none or only traces of β-mercaptoketones, diketones or alkanethiols were detected. The absence of alkanethiols indicated that 1,4-elimination of thioethers was not a major pathway for fragrance release. Extraction of the cotton sheets after analysis showed that thioethers were oxidised to sulfoxides, which then can generate enones by 1,4-elimination. Thioethers, sulfoxides and sulfones were shown to efficiently release enones in practical applications.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 6","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140571705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Total Synthesis of Core 3 & Core 4-Type Mucin Glycan Derivatives","authors":"Carmen R. Cori, Rachel Hevey","doi":"10.1002/hlca.202400026","DOIUrl":"10.1002/hlca.202400026","url":null,"abstract":"<p>Recent studies have demonstrated the ability of mucin O-glycans to attenuate virulence in diverse, cross-kingdom pathogens, sparking interest in their development as a novel therapeutic approach against infection. Although their virulence attenuating activity is evident, mucin glycans obtained from native sources comprise mixtures of several hundred distinct structures, and therefore the specific active glycan epitopes and molecular mechanisms of virulence attenuation remain unclear. Individual mucin glycan structures cannot be purified from native sources and are not amenable to automated synthesis; therefore, to further investigate the phenomena of virulence attenuation we have been developing convergent and scalable methods (>30 mg per target glycan) to assemble a mucin O-glycan library in sufficient scale and purity to facilitate biological studies. Previously we described a method to obtain core 1 & core 2-type mucin glycan derivatives that have since been used to identify active epitopes in <i>Candida albicans</i> and <i>Vibrio cholerae</i>. In the current study, we describe the expansion of our glycan library to include core 3 & core 4-type derivatives, increasing the structural diversity of our platform for biological evaluation.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 7","pages":""},"PeriodicalIF":1.5,"publicationDate":"2024-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400026","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140571667","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}
Jan-Simon Jeshua Friedrichs, Dr. Luca Schmermund, Dr. Corinna Urmann, Prof. Dr. Volker Sieber
{"title":"Synthesis of N-Substituted Pyrrole-2,5-dicarboxylic Acids from Pyrroles","authors":"Jan-Simon Jeshua Friedrichs, Dr. Luca Schmermund, Dr. Corinna Urmann, Prof. Dr. Volker Sieber","doi":"10.1002/hlca.202400036","DOIUrl":"10.1002/hlca.202400036","url":null,"abstract":"<p>Pyrrole-2,5-dicarboxylic acid (PDCA) is a heterocyclic aromatic dicarboxylic acid that may emerge as a new monomer for polyester production. Compared to its structurally related and bio-based furan-2,5-dicarboxylic acid (FDCA) that is already used for the production of polyethylene furanoate (PEF), PDCA shows excellent potential as its nitrogen can be targeted for further derivatization, thus enabling tuning of the properties of a PDCA containing polymer. In light of this, we recognized the need to explore efficient synthetic approaches for producing PDCAs in high yields. Here, we report a five-step synthesis route for <i>N</i>-substituted PDCAs starting from pyrrole, with total yields up to 42 %. The synthetic approach allowed the introduction of several different functional moieties to the pyrrole nitrogen, such as aliphatic saturated and unsaturated side-chains, as well as benzylic groups.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 6","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400036","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140571700","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":"Introduction for the Special Collection of Papers in the Honor of the President of the 56th Bürgenstock Conference, Alois Fürstner","authors":"Prof. Alois Fürstner","doi":"10.1002/hlca.202400042","DOIUrl":"10.1002/hlca.202400042","url":null,"abstract":"<p>\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400042","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140367343","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}
Erik Jung, Dr. Maja Hunter, Dr. Andrea Dorst, Alexander Major, Tatjana Teofilovic, Prof. Dr. Rolf Müller, Prof. Dr. Karl Gademann
{"title":"Isolation of Fidaxomicin and Shunt Metabolites from Actinoplanes deccanensis","authors":"Erik Jung, Dr. Maja Hunter, Dr. Andrea Dorst, Alexander Major, Tatjana Teofilovic, Prof. Dr. Rolf Müller, Prof. Dr. Karl Gademann","doi":"10.1002/hlca.202400013","DOIUrl":"10.1002/hlca.202400013","url":null,"abstract":"<p>A protocol for the isolation of the antibiotic fidaxomicin (Fdx) from <i>Actinoplanes deccanensis</i> and the isolation of shunt metabolites from <i>A. deccanensis fdxG2</i><sup><i>−</i></sup> is reported. We constructed the mutant strain <i>A. deccanensis fdxG2</i><sup><i>−</i></sup> by genetic manipulation which enabled the isolation of shunt metabolites as useful starting points for semisynthetic analogues of Fdx. Furthermore, a synthetic protocol for the conversion of complex <i>A. deccanensis fdxG2</i><sup><i>−</i></sup> extracts into the single compound FdxG2-OH <i>via</i> methanolysis is presented. This synthetic procedure is complemented by images and practical notes. Full structure assignment is given in the SI and the characterization data files are published to aid experimentalists. The protocol is also suitable as an undergraduate laboratory project. We hope to facilitate research into new Fdx derivatives through the availability of this procedure.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140202233","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":"Does the Central Nitrogen Atom Make a Difference? A Comparison of Non-Coordinating Pyridine and Benzene Spacers in Multitopic Ligands","authors":"Catherine E. Housecroft, Edwin C. Constable","doi":"10.1002/hlca.202400023","DOIUrl":"10.1002/hlca.202400023","url":null,"abstract":"<p>In metal coordination compounds of the divergent ligands 4,2′:6′,4“-terpyridine and 3,2′:6′,3”-terpyridine and their 4′-functionalized derivatives, the central pyridine ring of the 4,2′:6′,4“-terpyridine and 3,2′:6′,3”-terpyridine domains is non-coordinated. We present an overview of data from the Cambridge Structural Database to assess whether there are structural similarities between the coordination compounds of 4,2′:6′,4“-tpy and 1,3-di(pyridin-4-yl)benzene, and between 3,2′:6′,3”-tpy and 1,3-di(pyridin-3-yl)benzene. Based upon structurally characterized compounds, it emerges that the coordination chemistry of ligands including one or more 4,2′:6′,4“-terpyridine or 3,2′:6′,3”-terpyridine metal-binding domains is more abundantly exemplified than that of corresponding ligands based upon 1,3-di(pyridin-4-yl)benzene and 1,3-di(pyridin-3-yl)benzene. We provide an overview of metallamacrocycles and cages, 1D-coordination polymers and 2D- and 3D-networks.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140150151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Submonomer Synthesis of Inverse Polyamidoamine (i-PAMAM) Dendrimer Antibacterials","authors":"Hippolyte Personne, Xiaoling Hu, Etienne Bonvin, Jérémie Reusser, Jean-Louis Reymond","doi":"10.1002/hlca.202400041","DOIUrl":"10.1002/hlca.202400041","url":null,"abstract":"<p>Herein we report that the submonomer method for peptoid synthesis enables access to pure i-PAMAM dendrimers up to 16 amino termini by a divergent solid-phase synthesis using the inexpensive bis(3-trifluoroacetamidopropyl)amine as branching unit. We exemplify this new and efficient approach by a structure-activity relationship study of antibacterial dendrimers obtained by appending the polycationic i-PAMAM dendrimer to a hydrophobic core consisting of either an oligoleucine peptide or an oligo-<i>N</i>-isobutylglycine peptoid. These non-hemolytic dendrimers kill Gram-negative bacteria such as <i>Pseudomonas aeruginosa, Acinetobacter baumannii</i> and <i>Escherichia coli</i> as well as the Gram-positive methicillin-resistant <i>Staphylococcus aureus</i> (MRSA) by a non-membrane disruptive mechanism involving aggregation of intracellular content as reported for antimicrobial peptoids.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202400041","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140150144","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":"Protocol for the Photocatalytic Hydroxyalkenylation of Alkenes Using 1,2-Bis(phenylsulfonyl)ethylene and Water","authors":"Chen-Yang Tsai, Chun-Yu Chen, Yen-Ku Wu, Ilhyong Ryu","doi":"10.1002/hlca.202400017","DOIUrl":"10.1002/hlca.202400017","url":null,"abstract":"<p>We report on a protocol for the hydroxyalkenylation of alkenes using an acridinium photoredox catalyst in combination with 1,2-bis(phenylsulfonyl)ethylene and water. Using the protocol, alkenes could be converted into the corresponding 1-phenylsulfonyl-4-hydroxyalkenes in good yields. The hydroxyalkenylation involves the nucleophilic hydroxylation of alkene-derived radical cations to give β-hydroxyalkyl radicals, which then undergo a radical addition/β-elimination sequence. The catalytic cycle is likely sustained by electron transfer from the acridine radical to the benzenesulfonyl radical, which is formed via a radical addition/elimination sequence.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"107 5","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140128197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}