{"title":"Introduction for the Special Collection of Papers in the Honor of Robert Deschenaux.","authors":"Jean-François Nierengarten, Jean-Marie Lehn","doi":"10.1002/hlca.202300168","DOIUrl":"10.1002/hlca.202300168","url":null,"abstract":"<p>\u0000 \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":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202300168","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135590942","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}
Rocío Rivera Sánchez, Siva Bandi, Marie-Désirée Scheidt, Hanna Laaroussi, Bennett William Fox, Yojiro Ishida, Gaétan Glauser, Sylvain Sutour, Stephan H. von Reuss
{"title":"iso-Fatty Acid Metabolism in Caenorhabditis elegans’ Ceramide Biosynthesis","authors":"Rocío Rivera Sánchez, Siva Bandi, Marie-Désirée Scheidt, Hanna Laaroussi, Bennett William Fox, Yojiro Ishida, Gaétan Glauser, Sylvain Sutour, Stephan H. von Reuss","doi":"10.1002/hlca.202300131","DOIUrl":"10.1002/hlca.202300131","url":null,"abstract":"<p>Ceramide biosynthesis and its connection to iso-fatty acid metabolism in the model organism <i>Caenorhabditis elegans</i> was investigated using a combination of reverse genetics and comparative ESI-(+)-HR-MS<sup>e</sup> ceramide profiling along with incorporation experiments with bacterial mutants specifically enriched with isotopically labeled branched-chain amino acids or branched-chain fatty acids. Incorporation of a <span>l</span>-leucine-derived isovalerate unit into the conserved d17 : 1iso sphingosine building block proceeds through <i>elo-5</i> dependent chain elongation and depends on peroxisomal β-oxidation by the 3-ketoacyl-CoA thiolase <i>daf-22</i>, although ceramide profiles of N2 wildtype and <i>daf-22(ok693)</i> are indistinguishable. Biosynthesis of the homologous <i>N</i>-iso-acyl moieties also depends on <span>l</span>-leucine and isovalerate chain elongation but proceeds independently of <i>elo-5</i> and <i>daf-22</i>. Biosynthesis of the dominating <i>N</i>-docosanoyl moiety depends on <i>elo-3-</i>catalyzed chain elongation of bacteria-derived palmitic acid, whereas the <i>N</i>-tetracosanoyl moiety is derived from <i>de novo</i> lipogenesis.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202300131","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135805190","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}
Lee Pedzisa, Andrii Monastyrskyi, Camille D. Parker, William R. Roush
{"title":"Enantio- and Diastereoselective (Ipc)2BOTf-Mediated Aldol Reactions of Morpholine Carboxamides","authors":"Lee Pedzisa, Andrii Monastyrskyi, Camille D. Parker, William R. Roush","doi":"10.1002/hlca.202300126","DOIUrl":"10.1002/hlca.202300126","url":null,"abstract":"<p>Highly enantio- and diastereoselective (Ipc)<sub>2</sub>BOTf mediated aldol reactions of morpholine carboxamides are described. A wide variety of α-substituted <i>N</i>-acyl morpholine carboxamides were successfully employed, including α-bromo, α-chloro, α-vinyl and <i>para-</i>methoxyphenyl morpholine carboxamides which provided the corresponding aldol products in moderate to excellent yields, and generally with high enantio- and diastereoselectivities.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202300126","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135132429","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}
Zehua Ye, Jizeng Sun, Yujie Jin, Chuhao Lin, Jiyong Liu, Simon Duttwyler
{"title":"Synthesis of {CB11} Monocarborane Sulfonamides by B2-Selective Rhodium-Catalyzed B−H Activation","authors":"Zehua Ye, Jizeng Sun, Yujie Jin, Chuhao Lin, Jiyong Liu, Simon Duttwyler","doi":"10.1002/hlca.202300144","DOIUrl":"10.1002/hlca.202300144","url":null,"abstract":"<p>The synthesis of monocarborane sulfonamides is reported. The methodology relies on coupling of the anionic {CB<sub>11</sub>} boron cluster to sulfonyl azides. Under rhodium catalysis and with the assistance of a pyridine or pyrimidine directing group at the C1 position, the cluster undergoes B−H activation. Conditions have been identified that lead to B2-selective mono-sulfonamidation with concomitant loss of N<sub>2</sub>. The protocol requires no additional ligand, oxidant or base and enables B−N bond formation with various monocarborane and sulfonyl azide inputs. The new products possess the structure [1-(heteroaryl)-2-(NHSO<sub>2</sub>Ar)−CB<sub>11</sub>H<sub>10</sub>]<sup>−</sup> and have been fully characterized by NMR spectroscopy and mass spectrometry. In addition, three solid state structures confirm the particular B2 substitution pattern. Furthermore, the stoichiometric reaction of the pyridinyl monocarborane precursor with Rh(III) affords a cyclometalated complex with a direct B−Rh bond that has also been characterized by X-ray crystallography.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135385399","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}
Mengjie Hu, Mengjiao Zhu, Liying Ru, Jiangtao Ji, Ming Bao, Bo Peng
{"title":"Construction of Cyclobutane-Centered Tricyclic Caged Skeleton through a [5,5]-Rearrangement Triggered Cascade","authors":"Mengjie Hu, Mengjiao Zhu, Liying Ru, Jiangtao Ji, Ming Bao, Bo Peng","doi":"10.1002/hlca.202300149","DOIUrl":"10.1002/hlca.202300149","url":null,"abstract":"<p>In this report, we describe the combination of [5,5]-rearrangement-triggered dearomatization recently developed in our laboratory with an intramolecular formal [2+2]-cycloaddition for constructing an intriguing polysubstituted tricyclo[4.2.1.0<sup>3,8</sup>]nonane derivatives. The synthesis features the use of simple and readily available three distinct starting materials including aryl sulfoxides, allyl nitriles, and certain nucleophiles or dienes which directly enriches the diversity of target molecules. This study provides an entirely new protocol for the synthesis of cyclobutane-centered tricyclic caged skeleton.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135385661","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}
Alan M. Downward, Matteo Granelli, Celine Besnard, Laure Guénée, Alan F. Williams
{"title":"The Honeysuckle and the Bindweed Revisited: Synthesis and Stereochemistry of Extended Helical Structures from Coordination Complexes","authors":"Alan M. Downward, Matteo Granelli, Celine Besnard, Laure Guénée, Alan F. Williams","doi":"10.1002/hlca.202300120","DOIUrl":"10.1002/hlca.202300120","url":null,"abstract":"<p>We report structural studies of a chiral tridentate ligand which forms helical cubanes with cobalt(II) and manganese(II). A quadruple helicate with (<i>P</i>)<i>-</i>chirality is obtained using a (<i>S</i>)-ligand with cobalt(II) but the ligand binds manganese(II) in one of two possible orientations and either (<i>P</i>)<i>-</i> or (<i>M</i>)-quadruple helicates may be observed for a given ligand enantiomer. The helicates may be linked into extended structures by <i>p</i>-nitrobenzoate capping ligands which show stacking interactions with neighbouring complexes. With cobalt(II) we find an extended helical structure with (<i>M</i>)-chirality linking helicates which themselves have (<i>P</i>)<i>-</i>chirality. With manganese(II) we observe a remarkable structure with extended (<i>M</i>)-helices coexisting with extended (<i>P</i>)<i>-</i>helices.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202300120","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135386434","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}
Miguel López-Tena, Emma E. Watson, Patrick Romanens, Nicolas Winssinger
{"title":"Rapid Synthesis of Propargyl-γ-Modified Peptide Nucleic Acid Monomers for Late-Stage Functionalization of Oligomers","authors":"Miguel López-Tena, Emma E. Watson, Patrick Romanens, Nicolas Winssinger","doi":"10.1002/hlca.202300110","DOIUrl":"10.1002/hlca.202300110","url":null,"abstract":"<p>The exceptional hybridization properties of peptide nucleic acids (PNAs) coupled with the ease of their synthesis has made this artificial nucleic acid mimetic a desirable platform for diagnostics, therapeutics and supramolecular engineering. PNA backbone modifications have been extensively explored to finetune physicochemical properties and for conjugation of functional molecules. Here, we detail the synthesis of a universal γ-propargyl-PNA backbone from serine, and its acylation with the four DNA canonical nucleobases. The availability of serine as <span>d</span> or <span>l</span> enantiomer provide simple accesses to PNA oligomers for hybridization with natural oligonucleotides or for orthogonal hybridization circuitry. We show that late-stage conjugation enables optimization of the physicochemical properties. This approach is appealing due to its orthogonality to Fmoc-SPPS, its flexibility and ease for introducing diversity by on-resin copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). We exemplified the utility of these novel monomers with PNA based hybridization chain reactions (HCRs).</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202300110","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135536400","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":"β-Silylacrylate as a Multipurpose Reagent in Organic Synthesis","authors":"Sunil K. Ghosh","doi":"10.1002/hlca.202300141","DOIUrl":"10.1002/hlca.202300141","url":null,"abstract":"<p>Acrylates are well known electrophilic alkenes having multitude of applications in organic synthesis. They are very good acceptors in Michael addition reactions and are good enophile/dienophile/dipolarophile partners in cycloaddition reactions. Replacing the β-alkyl/aryl groups in acrylates by a silicon group would be interesting. In addition to the conventional reactions displayed by acrylates, β-silylacrylates (β-SAs) can show reactivity specifically related to the silicon group. Many conventional organic reactions such as hydrodimerization, organocatalytic asymmetric Michael additions, inter- and intra-molecular Diels–Alder reactions, and asymmetric 1,3-dipolar cycloadditions have been used to generate the complex chemical entities from β-SAs. Some of the reaction outcomes were vastly influenced by the silicon substituent. This review describes the practical synthesis β-SAs and their use as starting point in complex molecule generation including total synthesis of some natural products/bioactive molecules.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135815001","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}
Moritz Bernhardt, Lukas Lätsch, Boris Le Guennic, Christophe Copéret
{"title":"Identification of Favorable Silica Surface Sites for Single-Molecule Magnets","authors":"Moritz Bernhardt, Lukas Lätsch, Boris Le Guennic, Christophe Copéret","doi":"10.1002/hlca.202300130","DOIUrl":"10.1002/hlca.202300130","url":null,"abstract":"<p>Industrial data storage application based on single-molecule magnets (SMMs) necessitates not only strong magnetic remanence at high temperatures but also requires the implementation of SMMs into a solid material to increase their durability and addressability. While the understanding of the relationship between the local structure of the metal and the resulting magnetic behavior is well understood in molecular systems, it remains challenging to establish a similar understanding for magnetic materials, especially for isolated lanthanide sites on surfaces. For instance, dispersed Dy(III) ions on silica prepared <i>via</i> surface organometallic chemistry exhibit slow magnetic relaxation at low temperatures, but the origin of these properties remains unclear. In this work, we modelled ten neutral complexes with coordination numbers (CN) between three and six ([Dy(OSiF<sub>3</sub>)<sub>3</sub>(O(SiF<sub>3</sub>)<sub>2</sub>)<sub>CN-3</sub>]) representing possible surface sites for dispersed Dy(III) ions and investigated their SMM potential <i>via ab initio</i> CASSCF/RASSI-SO calculations. Detailed analysis of the data shows the strong influence of the spatial position of the anionic ligands while the neutral ligands only play a minor role for the magnetic properties. In particular, a T-shape like orientation of the anionic ligands is predicted to exhibit good SMM properties making it a promising targeted coordination environment for molecular and surface-based SMMs.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2023-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202300130","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135824310","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}