Helvetica Chimica Acta最新文献_第2页

Intramolecular Phenyl Transfer from Boron to Lithium, Sodium, and Copper: Defining the Limits of Transmetalation 从硼到锂、钠和铜的分子内苯基转移：确定金属转化的极限

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-04-22 DOI: 10.1002/hlca.202500049

Finn Kraft, Thomas Auth, Konrad Koszinowski

{"title":"Intramolecular Phenyl Transfer from Boron to Lithium, Sodium, and Copper: Defining the Limits of Transmetalation","authors":"Finn Kraft, Thomas Auth, Konrad Koszinowski","doi":"10.1002/hlca.202500049","DOIUrl":"https://doi.org/10.1002/hlca.202500049","url":null,"abstract":"Transmetalation is a key elementary step in organometallic chemistry, for which reason there is a keen interest in better understanding the factors governing this reaction. We have previously reported the unusual transfer of a phenyl anion from boron to lithium in the gas-phase dissociation of [LiBr(tBu)(Ph)Bpin]− (Chem. Eur. J. 2024, 43, e202303653). Here, we use a combination of gas-phase fragmentation experiments and quantum chemical calculations to probe the reactivity of the related adducts [MX(R)(Ph)Bpin]− (R=nBu, tBu, Ph; X=Cl, Br, I, BF4, BPh4; M=Li, Na, K, Cu). We find the transfer of Ph− to be much favored over that of nBu− and tBu−. The tendency toward transmetalation is decreased for anions X− that strongly bind to the metal center M. Likewise, it is diminished for more electropositive/less electronegative metals M. According to our theoretical calculations, the coordination of a single molecule of tetrahydrofuran to the metal M also lowers the propensity for transmetalation, thereby approaching the behavior in solution. Thus, our results reveal a subtle interplay of different effects influencing the tendency toward transmetalation.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 7","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500049","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647646","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

Cover Picture: (Helv. Chim. Acta 4/2025) 封面图片：（Helv.）詹。Acta 4/2025)

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-04-16 DOI: 10.1002/hlca.202570401

引用次数: 0

Synthesis, Characterization, and Biological Evaluation of Red Light-Activatable BODIPY-Caged Ceritinib Compounds 红光活化体吡啶笼状塞瑞替尼化合物的合成、表征及生物学评价

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-04-10 DOI: 10.1002/hlca.202500023

Kirill M. Kuznetsov, Kallol Purkait, Pierre Mesdom, Philippe Arnoux, Céline Frochot, Kevin Cariou, Gilles Gasser

{"title":"Synthesis, Characterization, and Biological Evaluation of Red Light-Activatable BODIPY-Caged Ceritinib Compounds","authors":"Kirill M. Kuznetsov, Kallol Purkait, Pierre Mesdom, Philippe Arnoux, Céline Frochot, Kevin Cariou, Gilles Gasser","doi":"10.1002/hlca.202500023","DOIUrl":"https://doi.org/10.1002/hlca.202500023","url":null,"abstract":"In this work, we aimed at photocaging the well-known anticancer agents dasatinib, ceritinib, gemcitabine, and combretastatin A4 with red-light activatable 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based cages using a carbonate/carbamate linking strategy. Due to the synthetic challenges discussed in this article, we only obtained two target compounds, namely two caged ceritinib compounds. The latter were characterized in-depth by nuclear magnetic resonance spectroscopy (NMR, 1H, COSY, 13C), high-resolution mass spectrometry (HRMS), infrared (IR) spectroscopy, and their purity was evaluated by elemental analysis. Their photophysical characteristics were also measured including absorption and emission spectra, quantum yields, and lifetimes. Analysis of the products after irradiation of the compounds allowed us to make assumptions about the possible mechanism of the phototransformations. Moreover, we conducted biological studies to determine the phototoxicity indexes of A549 cancer cells. While the two compounds were found to be non-toxic, the BODIPY precursors themselves were found to be highly toxic upon irradiation with phototoxicity indexes up to 1400.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 6","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500023","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292275","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

Blue Fluorescent Chlorophyll Catabolites from Banana Leaves Hypermodified with Terpenoidic Groups Related to Abscisic Acid 与脱落酸相关的萜类超修饰香蕉叶的蓝色荧光叶绿素分解代谢物

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-04-09 DOI: 10.1002/hlca.202500042

Clemens Vergeiner, Bernhard Kräutler

引用次数: 0

Breakable Nanomaterials to Allow Hair Coloring with Natural Dyes 易碎的纳米材料可以用天然染料染发

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-03-31 DOI: 10.1002/hlca.202500007

Giulia Coffetti, Giorgio Facchetti, Alessandro Ajò, Isabella Rimoldi, Luisa De Cola

引用次数: 0

Enhanced Photocatalytic Alkylation using Mg(SPh)2: The Role of Lewis Acidity in Catalyst Activity Mg(SPh)2增强光催化烷基化反应：刘易斯酸对催化剂活性的影响

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-03-29 DOI: 10.1002/hlca.202400207

Yasuhiro Yamashita, Tomoya Hisada, Yuki Sato, Shū Kobayashi

引用次数: 0

Photocleavable Porphyrin Derivatives for Quantum Optics 用于量子光学的光可切割卟啉衍生物

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-03-26 DOI: 10.1002/hlca.202500022

Olga Rybakova, Josef Reisinger, Philipp Rieser, Philipp Geyer, Stefan Gerlich, Markus Arndt, Amal Kumar, Daniel Häussinger, Marcel Mayor, Valentin Köhler

{"title":"Photocleavable Porphyrin Derivatives for Quantum Optics","authors":"Olga Rybakova, Josef Reisinger, Philipp Rieser, Philipp Geyer, Stefan Gerlich, Markus Arndt, Amal Kumar, Daniel Häussinger, Marcel Mayor, Valentin Köhler","doi":"10.1002/hlca.202500022","DOIUrl":"https://doi.org/10.1002/hlca.202500022","url":null,"abstract":"Optical control of molecular beams is intriguing as it promises to become a new tool for mass spectrometry and quantum interferometry, where a single or two photons deterministically remove a tailored tag from a larger molecular structure, e. g., a polypeptide. This cleavage process can change the charge state of the macromolecule, provide reporting signals for both fragments by mass spectrometry and it can selectively remove the fragments from a molecular beam by the momentum recoil generated in the dissociation process. Here, we explore a series of porphyrin derivatives as candidates for photocleavage in the gas phase. They share a large, conjugated core which promises a high absorption cross section for visible light. We present the individualization and beam formation of candidate molecules and study their photo-dissociation under tunable, visible radiation. We observe a significant wavelength shift and broadening in the photocleavage cross section for molecules in the gas phase compared to those in solution and we find that a single photon can suffice to trigger the cleavage process.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 5","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/hlca.202500022","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074716","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

Effect of Gel Alkalinity on the Catalytic Properties of PdCu/NaY Zeolites for Methyl Nitrite Carbonylation to Dimethyl Carbonate 凝胶碱度对PdCu/NaY分子筛催化亚硝酸盐甲酯羰基化制碳酸二甲酯性能的影响

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-03-25 DOI: 10.1002/hlca.202500015

Sendaner Adelieti, Si-Qi Wu, Xian-Hao Wu, Rong Guo, Jian-Shan Chen, Zhi-Fang Diao, Zi-Yi Miao, Zhen-Hong Han, Ye-Yan Qin, Yuan-Gen Yao

{"title":"Effect of Gel Alkalinity on the Catalytic Properties of PdCu/NaY Zeolites for Methyl Nitrite Carbonylation to Dimethyl Carbonate","authors":"Sendaner Adelieti, Si-Qi Wu, Xian-Hao Wu, Rong Guo, Jian-Shan Chen, Zhi-Fang Diao, Zi-Yi Miao, Zhen-Hong Han, Ye-Yan Qin, Yuan-Gen Yao","doi":"10.1002/hlca.202500015","DOIUrl":"https://doi.org/10.1002/hlca.202500015","url":null,"abstract":"The carbonylation of methyl nitrite (MN) to synthesize dimethyl carbonate (DMC) is a promising route, but the lack of efficient and stable catalysts remains a major challenge for large-scale applications. In this study, by adjusting the alkalinity of the initial gel, NaY zeolites with tunable acidity were synthesized, and the amount of Lewis acid sites was optimized. Appropriate amounts of Lewis acid sites facilitated the interaction between NaY zeolites and Pd species, which was beneficial for stabilizing the oxidation state of Pd and promoting CO adsorption and activation, thereby contributing to the formation of the key intermediate *COOCH3. The catalyst PdCu/NaY-1 (alkalinity in the initial gel Na2O=9) exhibited significant improvement in catalytic performance for the synthesis of DMC, with the WTYDMC of 1604 g kgcat−1⋅h−1, the conversion of CO to DMC (CCO) of 88.7 %, and the DMC selectivity based on CO (SDMC/CO) up to 100 %.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 6","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144292946","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

Understanding the Structure of Protonated Box Ligands: Insights from Spectroscopy and Computational Studies 理解质子化盒子配体的结构：来自光谱学和计算研究的见解

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-03-23 DOI: 10.1002/hlca.202400205

Vladimir Gorbachev, Lara van Tetering, Jonathan Martens, Jos Oomens, Giel Berden, Alexandra Tsybizova, Peter Chen

{"title":"Understanding the Structure of Protonated Box Ligands: Insights from Spectroscopy and Computational Studies","authors":"Vladimir Gorbachev, Lara van Tetering, Jonathan Martens, Jos Oomens, Giel Berden, Alexandra Tsybizova, Peter Chen","doi":"10.1002/hlca.202400205","DOIUrl":"https://doi.org/10.1002/hlca.202400205","url":null,"abstract":"Protonation and tautomerization significantly impact the conformational landscape and non-covalent interactions in bis(oxazoline) (BOX) ligands, which are crucial for their applications in catalysis. These interactions influence properties such as binding affinity and catalytic efficiency. While tautomerization has been reported for neutral BOX ligands, its role in protonated forms remains less understood. Here we report the structural and spectroscopic characterization of (S,S−Ph-BOX)H+ and its tautomerization-resistant derivative (S,S−Ph-diMeBOX)H+. We show through IRMPD spectroscopy and TIMS experiments, combined with DFT calculations that (S,S−Ph-BOX)H+ is present in its tautomeric form, while a broader conformational landscape is observed for (S,S−Ph-diMeBOX)H+, in which an N−H⋅⋅⋅N proton-shared conformer is identified. These findings provide a deeper understanding of the relationship between tautomerization and non-covalent interactions in protonated BOX ligands, offering insights for the design of catalytic systems.","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 5","pages":""},"PeriodicalIF":1.5,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074773","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

Approaches to Commercial Sandalwood Odorants from Renewable Sources 从可再生资源中提取商用檀香气味剂的方法

IF 1.5 4区化学

Helvetica Chimica Acta Pub Date : 2025-03-19 DOI: 10.1002/hlca.202500010

Anthony A. Birkbeck, Christian Chapuis, Michel Schalk

引用次数: 0