Helvetica Chimica Acta最新文献_第8页

Spirocyclic Diamine Scaffolds for Medicinal Chemistry 药物化学用螺环二胺支架

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-12-08 DOI: 10.1002/hlca.202500207

Aline Carrel, Alejandro Flores, Maedeh Darsaraee, Jean-Louis Reymond

引用次数: 0

Xanthate-Based Pathways to Ketones 以黄原酸为基础的酮途径

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-12-05 DOI: 10.1002/hlca.202500197

Samir Z. Zard

引用次数: 0

Controlling Rotational Motion of Nonplanar Porphyrin Atropisomers by Metal Coordination 金属配位控制非平面卟啉反映体的旋转运动

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-12-05 DOI: 10.1002/hlca.202500192

Sophie Maguire, John E. O'Brien, Brendan Twamley, Liam Cribbin, Mathias O. Senge

{"title":"Controlling Rotational Motion of Nonplanar Porphyrin Atropisomers by Metal Coordination","authors":"Sophie Maguire, John E. O'Brien, Brendan Twamley, Liam Cribbin, Mathias O. Senge","doi":"10.1002/hlca.202500192","DOIUrl":"https://doi.org/10.1002/hlca.202500192","url":null,"abstract":"Porphyrin atropisomerism is an outstanding tool for the accessibility of shape-specific molecules, yet over 20 years after the unusual rotational barriers of nonplanar porphyrins were observed, a quantitative relationship remains at large. There is a growing need to control this phenomenon in nonplanar porphyrin systems due to the mounting interest in these systems as enzyme mimics and organocatalysts. Hence, in this work, the influence of steric bulk on the stability of nonplanar 5,10,15,20-tetraaryl-2,3,7,8,12,13,17,18-octaethyl-porphyrin atropisomers was explored. The library of atropisomeric porphyrins synthesized herein emphasizes the delicate balance that must be achieved between steric bulk without inducing an undesired amount of macrocycle flexibility to obtain an atropisomer with a predictable rotational barrier. To overcome this challenge, a stabilization strategy was devised by exploiting metal coordination to the peripheral porphyrin functionalities, leading to an atroposelective superstructure formation.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500192","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145986824","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

Tuning Pore Chemistry in Dioxin-Linked Porous Organic Polymers for Enhanced High-Pressure CO2 Uptake 调节二恶英连接的多孔有机聚合物的孔隙化学以增强高压CO2吸收

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-12-03 DOI: 10.1002/hlca.202500174

Timur Ashirov, Krzysztof Piech, Onur Buyukcakir, Taner Yildirim, Ali Coskun

{"title":"Tuning Pore Chemistry in Dioxin-Linked Porous Organic Polymers for Enhanced High-Pressure CO2 Uptake","authors":"Timur Ashirov, Krzysztof Piech, Onur Buyukcakir, Taner Yildirim, Ali Coskun","doi":"10.1002/hlca.202500174","DOIUrl":"https://doi.org/10.1002/hlca.202500174","url":null,"abstract":"Precise tuning of pore chemistry in three-dimensional porous organic polymers (3D-POPs) is critical for high-performance gas (CO2)-separation. Here, we demonstrate the impact of functional groups on the dioxin-linked 3D-tPOPs bearing a tetraphenylene core, synthesized under solvothermal conditions using NaCl as a template, on the low- and high-pressure CO2 uptake. The post-synthetic amidoxime functionalization of 3D-tPOPs, involving the reaction of pendant nitrile moieties with hydroxylamine hydrochloride, has been shown to precisely tailor pore chemistry without altering the network structure. Whereas the incorporation of the amidoxime moieties, 3D-tPOP-AO, enables higher heteroatom content, a critical factor to enhance CO2 affinity at low pressures, strong hydrogen bonding interactions between amidoxime units limit framework flexibility, thus leading to a significant decrease in the high-pressure gas uptake. 3D-tPOPs on the other hand showed a high CO2 uptake capacity of 57.4 wt% at 33 bar and 270 K; after modification, CO2 uptake capacity decreased to 19.4 wt% at 273 K and 34 bar. Similarly, CH4 uptake capacity also decreased from 14.0 wt% at 116 bar and 270 K to 3.8 wt% at 75 bar and 273 K. These findings highlight the critical role of the interactions between functional groups and pore chemistry to form robust adsorbents with high CO2 uptake performance at high pressures.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500174","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993914","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

Scalable Synthesis of Highly Pure (R)-3-Fluoropyrrolidine From (S)-4-Chloro-3-hydroxybutyronitrile 由(S)-4-氯-3-羟基丁腈可扩展合成高纯(R)-3-氟吡咯烷

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-11-30 DOI: 10.1002/hlca.202500164

Christian P. Bold, Pascal S. Engl, Alfred Stutz, Markus Stöckli, Matthias Krämer, Serena M. Fantasia, Albrecht Metzger, Christian Moessner, Paolo Tosatti, Stefan Hildbrand

{"title":"Scalable Synthesis of Highly Pure (R)-3-Fluoropyrrolidine From (S)-4-Chloro-3-hydroxybutyronitrile","authors":"Christian P. Bold, Pascal S. Engl, Alfred Stutz, Markus Stöckli, Matthias Krämer, Serena M. Fantasia, Albrecht Metzger, Christian Moessner, Paolo Tosatti, Stefan Hildbrand","doi":"10.1002/hlca.202500164","DOIUrl":"https://doi.org/10.1002/hlca.202500164","url":null,"abstract":"<div>\u0000 \u0000 (S)-Pyrrolidin-3-ol and (R)-3-fluoropyrrolidine are key intermediates in Roche's drug candidates, Vicasinabin and Mosperafenib. Sourcing these compounds proved challenging, particularly for (R)-3-fluoropyrrolidine, for which a quality of ≥ 99.8% purity and ≥ 99.95% chiral purity along with stringent impurity control was required. To address these challenges, a scalable process for the manufacturing of (R)-3-fluoropyrrolidine hydrochloride salt using a stereoselective SN2 reaction was developed based on prior work on (S)-pyrrolidin-3-ol synthesis. The process was successfully scaled up in the pilot plant, enabling the production of a total of 798 kg of high-purity (R)-3-fluoropyrrolidine hydrochloride salt to support the clinical development of Mosperafenib. Key steps included “pump-hydrogenation” to improve the yield of (S)-pyrrolidin-3-ol from the cost-effective starting material (S)-4-chloro-3-hydroxybutyronitrile. This was followed by in situ Boc-protection, and a two-step stereospecific fluorination involving mesylation and nucleophilic substitution with potassium fluoride. Finally, Boc-deprotection using HCl followed by recrystallization from n-BuOH and water, ensured efficient removal of impurities including the undesired enantiomer. This streamlined approach addressed supply challenges, ensured consistent quality, and established an efficient, robust manufacturing process for (R)-3-fluoropyrrolidine hydrochloride.\u0000 </div>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145994015","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

Allylation of C(sp3)─H Bonds Using a MW/Persulfate Protocol 用MW/过硫酸盐协议进行C（sp3）─H键烯丙基化

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-11-29 DOI: 10.1002/hlca.202500191

Hsin-Hsuan Lee, Chun-Yu Chen, Yen-Ku Wu, Ilhyong Ryu

引用次数: 0

Bismuth Compounds React With a Nitrone: Lewis Pair Formation and Quantification of Radical Trapping 铋化合物与硝酮反应：路易斯对的形成和自由基俘获的定量

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-11-29 DOI: 10.1002/hlca.202500182

Andreas Stoy, Johannes Schwarzmann, Felix Geist, Ahmed Fetoh, Malte Jürgensen, Jordi Poater, Istemi Kuzu, Crispin Lichtenberg

{"title":"Bismuth Compounds React With a Nitrone: Lewis Pair Formation and Quantification of Radical Trapping","authors":"Andreas Stoy, Johannes Schwarzmann, Felix Geist, Ahmed Fetoh, Malte Jürgensen, Jordi Poater, Istemi Kuzu, Crispin Lichtenberg","doi":"10.1002/hlca.202500182","DOIUrl":"https://doi.org/10.1002/hlca.202500182","url":null,"abstract":"Reactions of the Lewis acidic, cationic bismuth compound [BiMe2(SbF6)] (1) with the spin trap α-phenyl-N-tertbutyl-nitrone (PBN) yield simple Lewis acid/base adducts [BiMe2(PBN)(SbF6)] (2) and [BiMe2(PBN)2][SbF6] (3). Such adducts have, for the first time, been fully characterized for the frequently used spin trap PBN. The ability of 2 and 3 to release PBN-trapped methyl radicals under thermal conditions is investigated. This is compared to the ability of a small series of simple neutral organobismuth compounds BiR3 (R = Me, nBu, iPr, tBu, CF3) and one mixed aryl/alkyl-substituted bismuth complex to transfer carbon-based radicals to PBN. Applied analytical techniques include NMR spectroscopy, elemental analysis, mass spectrometry, single-crystal X-ray diffraction analysis, and EPR spectroscopy.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"109 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500182","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145987124","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

Photo-Flow Reaction and Enantiomer Separation as an Enabling Combination to Chiral Substituted 1,2-Cyclobutanediol 光流反应和对映体分离是手性取代1,2-环丁二醇的有利组合

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-11-21 DOI: 10.1002/hlca.202500200

Antony Bigot, François Decalogne, Jésus Manzanas, Changxia Yuan, Han Chen, Fenglai Sun

引用次数: 0

Cell-Penetrating Poly(disulfide)s Cell-Penetrating聚(二硫)

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-11-14 DOI: 10.1002/hlca.202500129

Michael Cognet, Giacomo Renno, Nicholas Rose, Yuheng Zhang, Pierre Josso, Julia Moreno, Xudong Ren, Jules Bouffard, Saidbakhrom Saidjalolov, Naomi Sakai, Stefan Matile

{"title":"Cell-Penetrating Poly(disulfide)s","authors":"Michael Cognet, Giacomo Renno, Nicholas Rose, Yuheng Zhang, Pierre Josso, Julia Moreno, Xudong Ren, Jules Bouffard, Saidbakhrom Saidjalolov, Naomi Sakai, Stefan Matile","doi":"10.1002/hlca.202500129","DOIUrl":"https://doi.org/10.1002/hlca.202500129","url":null,"abstract":"To appreciate 10 years of cell-penetrating poly(disulfide)s (CPDs), this review comprehensively covers the structures realized by now. CPDs have been introduced as dynamic covalent polymers that i) are obtained from cyclic disulfide monomers by ring-opening polymerization (ROP) and ii) enter cells by thiol-mediated uptake. They were discovered in 2014 and have been used since then for diverse delivery applications in vitro and in vivo. The introduction briefly sketches their mode of action, as far as it is known. The main part lists the CPDs realized so far, organized by their structures, with selected examples for biological applications. The final chapters cover the few cyclic monomers other than lipoic acid derivatives that have been explored and links to related topics such as templated ROP of cyclic disulfides in lipoplexes and liposomes and related delivery motifs. We hope this review offers a solid and productive basis for future progress with CPD research and its use in science and society.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 12","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500129","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145761149","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

Air-Stable Aluminum Tris[Bis(mesitoyl)Arsenide] Precursor for Metal Arsenide Quantum Dots 金属砷量子点的空气稳定铝三[双（甲酰基）砷化]前驱体

IF 1.8 4区化学

Helvetica Chimica Acta Pub Date : 2025-11-14 DOI: 10.1002/hlca.202500162

Georgian Nedelcu, Sergii Yakunin, Artem Yanchak, Matthias Driess, Hansjörg Grützmacher, Dmitry N. Dirin, Maksym V. Kovalenko

{"title":"Air-Stable Aluminum Tris[Bis(mesitoyl)Arsenide] Precursor for Metal Arsenide Quantum Dots","authors":"Georgian Nedelcu, Sergii Yakunin, Artem Yanchak, Matthias Driess, Hansjörg Grützmacher, Dmitry N. Dirin, Maksym V. Kovalenko","doi":"10.1002/hlca.202500162","DOIUrl":"https://doi.org/10.1002/hlca.202500162","url":null,"abstract":"Colloidal III–V arsenide quantum dots (QDs) are promising low-toxicity, solution-processable materials for near-infrared optoelectronics, yet their development has been constrained by the scarcity of suitable precursors and proneness to oxidation. Existing routes either rely on highly reactive but toxic, pyrophoric group-14-substituted arsines, or on safer aminoarsines that require in situ reduction and cause staggered rather than a single burst nucleation. We introduce aluminum tris[bis(mesitoyl)arsenide] as a nonpyrophoric and air-stable precursor that, upon nucleophilic attack, directly delivers the formally As3− species. Using this precursor, we synthesized 2.3–4.6 nm large InAs QDs and 2–5.5 nm large Cd3As2 QDs with photoluminescence tunable in the 800–2250 nm range. These results establish aluminum tris[bis(mesitoyl)arsenide] as a versatile precursor, enabling safe and controlled syntheses of various arsenide QDs.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 12","pages":""},"PeriodicalIF":1.8,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500162","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145761148","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