Helvetica Chimica Acta最新文献

Systematic Evaluation of Electrophile Reactivity and Stability for Covalent DNA-Encoded Libraries 共价dna编码文库亲电反应性和稳定性的系统评价

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-03-20 DOI: 10.1002/hlca.70064

Johanna Puff, Giulia Assoni, Jiannan Zhao, Qi Zhang, Zhongyao Ma, Huan Liu, Weiren Cui, Alexander L. Satz, Wenji Su, Letian Kuai, Andreas Gloger, Jörg Scheuermann

{"title":"Systematic Evaluation of Electrophile Reactivity and Stability for Covalent DNA-Encoded Libraries","authors":"Johanna Puff, Giulia Assoni, Jiannan Zhao, Qi Zhang, Zhongyao Ma, Huan Liu, Weiren Cui, Alexander L. Satz, Wenji Su, Letian Kuai, Andreas Gloger, Jörg Scheuermann","doi":"10.1002/hlca.70064","DOIUrl":"https://doi.org/10.1002/hlca.70064","url":null,"abstract":"DNA-encoded Chemical Libraries (DEL) are increasingly being used for the discovery of new covalent drugs. In the work presented here, we describe a systematic study that investigates the suitability of a selection of 59 electrophilic compounds for the construction of versatile covalent DNA-encoded libraries. We investigated six classes of electrophilic warheads with the potential to form irreversible covalent bonds with a nucleophilic target, that is, aryl halides, alkenes, alkynes, epoxides, α-chloro carboxylates, and aromatic methylsulfonates, as well as two classes of electrophiles capable of forming reversible covalent bonds, that is, aldehydes and nitriles. The electrophiles were successively tested for their capability to be installed on DNA, their stability as DNA-conjugates under various storage conditions, and, ultimately, for their on-DNA reactivity and selectivity toward S-nucleophiles (cysteine) and N-nucleophiles (lysine). Eventually, 21 DNA-linked electrophiles with favorable properties were identified, with over 50% coupling to DNA, excellent storage stability, and high reactivity toward either S- or both S- and N-nucleophilic substrates.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.70064","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686211","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}

引用次数: 0

High-Resolution Ion Mobility Approach for Rapid Determination of Multiple Human Milk Oligosaccharide Isomer Ratios 高分辨率离子迁移率法快速测定多种人乳寡糖异构体比例

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-03-10 DOI: 10.1002/hlca.202500232

Wenqing Xu, Estelle Rathahao-Paris, Blanche Guillon, François Fenaille, Karine Adel-Patient, Sandra Alves

引用次数: 0

Monosaccharide-Based Macrocyclic Receptors—History and Recent Applications 基于单糖的大环受体的历史和最新应用

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-03-13 DOI: 10.1002/hlca.202500219

Bartosz Lewandowski

引用次数: 0

Mapping Alkyne Chemical Space—Classifying the Reactivity of Alkynes in Semihydrogenation and beyond Using a Data Science Framework 炔化学空间的映射——用数据科学框架对炔半氢化及其后反应性进行分类

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-02-16 DOI: 10.1002/hlca.202500166

Jordan De Jesus Silva, Scott R. Docherty, Jasper Clarysse, Maksym Yarema, Vanessa Wood, Christophe Copéret

{"title":"Mapping Alkyne Chemical Space—Classifying the Reactivity of Alkynes in Semihydrogenation and beyond Using a Data Science Framework","authors":"Jordan De Jesus Silva, Scott R. Docherty, Jasper Clarysse, Maksym Yarema, Vanessa Wood, Christophe Copéret","doi":"10.1002/hlca.202500166","DOIUrl":"https://doi.org/10.1002/hlca.202500166","url":null,"abstract":"A data science framework that integrates DFT featurization, dimensionality reduction, and hierarchical clustering is employed to study the chemical space of commercially available alkynes, highlighting the differentiation of over 2700 structures into 6 subsets. Referencing the substrate scope of a recent publication, the selected molecules are shown to be representative of the alkyne chemical space by covering each of the 6 clusters. Logistic regression classification allows the categorization of the tested alkynes according to their propensity to hydrogenate under milder or harsher reaction conditions. This categorization identified highly chemically shielded alkynes with low total dipole as the easiest to hydrogenate, likely by breaking the cylindrical symmetry of the alkyne. In summary, we identify potential reasons for the difference in reactivity of alkyne substrates in Ni3Zn nanocrystal catalyzed semi-hydrogenation and present a useful workflow and alkyne data set for studying catalytic reactions in general.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500166","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686303","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}

引用次数: 0

Intramolecular C–H Nitrene Insertion Catalyzed by Single-Atom Cobalt on Nitrogen-Doped Carbon 单原子钴在氮掺杂碳上催化的分子内C-H亚硝基插入

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-03-25 DOI: 10.1002/hlca.202500228

Tomohiro Yasukawa, Yuki Nakao, Yasuhiro Yamashita, Muneaki Yamamoto, Tomoko Yoshida, Shū Kobayashi

引用次数: 0

Electrochemical Generation of N-Centered Radicals and Their Reactivity Toward Cyclization and Subsequent C─C Bond Cleavage n中心自由基的电化学生成及其对环化和随后的C─C键裂解的反应性

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-03-04 DOI: 10.1002/hlca.202500225

Sharad M. Suryawanshi, Mayuri Singh, Ramesh C. Samanta

{"title":"Electrochemical Generation of N-Centered Radicals and Their Reactivity Toward Cyclization and Subsequent C─C Bond Cleavage","authors":"Sharad M. Suryawanshi, Mayuri Singh, Ramesh C. Samanta","doi":"10.1002/hlca.202500225","DOIUrl":"https://doi.org/10.1002/hlca.202500225","url":null,"abstract":"<div>\u0000 \u0000 N-containing heterocycles are widely used in medicinal chemistry, and they can be synthesized efficiently by the intramolecular cyclization of N-centered radicals. Furthermore, N-centered radicals also act as excellent hydrogen atom transfer (HAT) reagents. On the other hand, nitrogen atoms in the nitrogen-containing heterocycles are used as a handle to cleave stable five and six-membered rings. However, the electrochemical generation of N-centered radicals and their application in forming heterocycles have been extensively studied. Study beyond cyclization remains largely unexplored; in this manuscript, we summarize our new findings as follows. Under electrochemical conditions, the N─H bond is cleaved, forming an N-centered radical that adds to the double bond in a 6-endo-trig cyclization fashion. The newly formed C-centered radical reacts with oxygen and undergoes C─C bond cleavage to form the corresponding carbonyl compounds. The reactivity is dependent on the substituents present on nitrogen. In the case of aromatic amine-derived amide, the TEMPO trapping cyclization product was isolated. A mechanism has been proposed to explain the formation of the products.\u0000 </div>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686895","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}

引用次数: 0

Streamlined Synthesis of Triamantane from Readily Available Starting Materials 从现成原料流线型合成三金刚烷

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-02-07 DOI: 10.1002/hlca.70057

Xiao-Yu Li, Christof Sparr

{"title":"Streamlined Synthesis of Triamantane from Readily Available Starting Materials","authors":"Xiao-Yu Li, Christof Sparr","doi":"10.1002/hlca.70057","DOIUrl":"https://doi.org/10.1002/hlca.70057","url":null,"abstract":"As molecular fragments of diamond, diamondoids represent a unique class of cage hydrocarbons with extreme rigidity, stability, and ideal biocompatibility. Together with adamantane and diamantane, triamantane belongs to the lower diamondoids, which are favorable precursors for a diversity of applications in medicinal chemistry and materials science, or as gateway to synthetic higher diamondoids. After employing triamantane in the synthesis of skew-tetramantane, we now report a practical synthetic procedure based on McKervey's variation of Schleyer's stabilomeric synthesis and the versatile chemistry enabled by the norbornadiene dimer Binor-S. After optimization, a Binor-S rearrangement and subsequent Diels–Alder reaction with a readily available solution of butadiene allowed to prepare triamantane in synthetically meaningful yields on a tens-of-grams scale. Building on the concept of stabilomeric synthesis, streamlining the route to triamantane provides an alternative to its isolation from fossil fuels and enables diverse applications of triamantane or the synthesis of higher diamondoids, such as skew-tetramantane.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.70057","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686158","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}

引用次数: 0

Formal Synthesis of the Akuammiline Alkaloid (±)-Strictamine via a (4 + 2) Annulation Reaction With a Donor–Acceptor Cyclobutane 与供体-受体环丁烷（4 + 2）环化反应正式合成（±）-蛇胺

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-01-30 DOI: 10.1002/hlca.202500163

Clément Tanguy, Emma G. L. Robert, Jerome Waser

引用次数: 0

How (not) to Cage an Electron: The Perfluoro Cage Effect as an Extrinsic Molecular Property 如何（不）笼养电子：全氟笼效应作为一种外在分子性质

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-02-28 DOI: 10.1002/hlca.202500179

Andreas Riedmiller, Christian Mück-Lichtenfeld, Johannes Neugebauer

{"title":"How (not) to Cage an Electron: The Perfluoro Cage Effect as an Extrinsic Molecular Property","authors":"Andreas Riedmiller, Christian Mück-Lichtenfeld, Johannes Neugebauer","doi":"10.1002/hlca.202500179","DOIUrl":"https://doi.org/10.1002/hlca.202500179","url":null,"abstract":"The notion of a (molecular) electron cage was coined for the unique hosting capacity of perfluorocubane, suggesting the “encapsulation of an electron” within the highly symmetric molecular framework. Extensions to this occurrence of a perfluoro cage effect (PCE) have been found in a variety of different cage structures, showing a remarkable transferability within the chemical subspace of perfluorinated prismanes and fullerens. Classifications of this cage effect based on Sigma Stellation fail for extended carbon frameworks, whereas Baders Atoms-in-Molecules analysis of non-nuclear attractors is inconclusive for smaller systems. Our investigation of the electronic structure within the molecular cage of perfluorocubane does not support the hypothesis of a caged electron as the common cause of the unique electron affinity characteristic for the PCE. Instead, we observe a central confining nodal surface within the spin density for perfluorocubane, which also occurs for any other radical anion of the aforementioned chemical subspace considered here. The association of the spin density to the singly occupied molecular orbital of a corresponding restricted-open-shell Kohn–Sham reference system enables us to construct a quantitative single-particle model that captures the main tendencies of the vertical electron affinity on the symmetry and size of the system. The derivation is based on the so-called nodal variational principle and thereby clarifies the effectiveness of a confined particle model for the PCE without any reference to the encapsulation of an electron.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500179","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686307","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}

引用次数: 0

Diterpenoid Diversity across Land Plants 陆地植物的二萜多样性

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2026-04-16 Epub Date: 2026-02-23 DOI: 10.1002/hlca.202500222

Anita Berg, Chad K. Papenfuhs, Amy E. Fraley

{"title":"Diterpenoid Diversity across Land Plants","authors":"Anita Berg, Chad K. Papenfuhs, Amy E. Fraley","doi":"10.1002/hlca.202500222","DOIUrl":"https://doi.org/10.1002/hlca.202500222","url":null,"abstract":"The diverse array of diterpenoid natural products stems from the ease of manipulating the promiscuity of diterpene cyclases. These enzymes are able to generate a vast array of structurally distinct diterpene skeletons from a common precursor, such as geranylgeranyl diphosphate, through subtle modifications in their active sites. Even minor amino acid substitutions can reshape the contour of the active site or alter the stabilization of key carbocation intermediates, leading to the emergence of new product profiles. This capacity for functional plasticity allows diterpene cyclases to rapidly explore chemical space, providing a rich assortment of scaffolds for development and persistence via natural selection. As a result, gene duplication followed by neofunctionalization of diterpene cyclases has driven the expansion of terpenoid repertoires across plant lineages, contributing to ecological diversification and specialized metabolic functions such as defense, communication, and adaptation to environmental stress. Here we will focus on the understudied bryophyte terpenome from structural diversification at the molecular level to regulation of biosynthetic pathways at the macroorganism level.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 4","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500222","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147686336","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}

引用次数: 0