Joseph Ford, Benjamin Hopkin, Jeroen B. I. Sap, Véronique Gouverneur
Herein, we report a minimalistic protocol for the solvent-free, mechanochemical difluoromethylation of (thio)phenols and N-heteroarenes using non-ozone depleting chlorodifluoromethyl phenyl sulfone as a difluorocarbene source. This mechanochemical difluoromethylation features a short reaction time, excellent functional group tolerance, and compatibility with complex biologically active scaffolds.
{"title":"Mechanochemical difluoromethylation of (thio)phenols and N-heterocycles","authors":"Joseph Ford, Benjamin Hopkin, Jeroen B. I. Sap, Véronique Gouverneur","doi":"10.1002/ijch.202300109","DOIUrl":"10.1002/ijch.202300109","url":null,"abstract":"<p>Herein, we report a minimalistic protocol for the solvent-free, mechanochemical difluoromethylation of (thio)phenols and <i>N</i>-heteroarenes using non-ozone depleting chlorodifluoromethyl phenyl sulfone as a difluorocarbene source. This mechanochemical difluoromethylation features a short reaction time, excellent functional group tolerance, and compatibility with complex biologically active scaffolds.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2023-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202300109","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135736046","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}
Transition metal catalysts with modified second-coordination sphere employed in the electrocatalytic CO2 can result in increased activity or directed product selectivity. Calixarenes can form metal complexes and potentially catalyze reactions within its cavity, taking advantage of the surrounding phenols groups to tune the reactivity by second-coordination sphere effects. Here, we present a Mn(I) bromotricarbonyl complex with phenanthroline-functionalized calix[8]arene ligands capable of electrocatalytically reducing CO2 into different products with 2,2,2-trifluoroethanol as proton donor. The selectivity of the reaction seems to be affected by the calixarene cavity: two calixarene-free analogous complexes reduce CO2 to CO almost exclusively, while the calixarene complexes produce primarily CO, H2. Interestingly, in some cases the less frequently observed CH4 was also detected, albeit with low Faradaic efficiency. Thus, the manganese center placed within the calixarene cavity promotes the formation of reduced CO2 products by more than two electrons and two protons, affording CH4 in some cases.
在电催化 CO2 中使用具有改性第二配位层的过渡金属催化剂可以提高活性或定向产品选择性。六碳烯可以形成金属配合物,并有可能在其空腔内催化反应,利用周围的酚基,通过第二配位层效应来调节反应活性。在此,我们介绍了一种具有菲罗啉功能化钙[8]烯配体的溴羰基锰(I)配合物,该配合物能够以 2,2,2-三氟乙醇为质子供体,通过电催化将 CO2 还原成不同的产物。反应的选择性似乎受到钙[8]烯空腔的影响:两种不含钙[8]烯的类似配合物几乎只将 CO2 还原成 CO,而钙[8]烯配合物则主要生成 CO 和 H2。有趣的是,在某些情况下还能检测到不太常见的 CH4,尽管法拉第效率较低。因此,放置在钙铝烯烃空腔中的锰中心通过两个以上的电子和两个质子促进了还原 CO2 产物的形成,在某些情况下产生了 CH4。
{"title":"Calix[8]arene-Based Manganese Complexes for Electrocatalytic CO2 Reduction","authors":"Armando Berlanga-Vázquez, Ivan Castillo","doi":"10.1002/ijch.202300083","DOIUrl":"10.1002/ijch.202300083","url":null,"abstract":"<p>Transition metal catalysts with modified second-coordination sphere employed in the electrocatalytic CO<sub>2</sub> can result in increased activity or directed product selectivity. Calixarenes can form metal complexes and potentially catalyze reactions within its cavity, taking advantage of the surrounding phenols groups to tune the reactivity by second-coordination sphere effects. Here, we present a Mn(I) bromotricarbonyl complex with phenanthroline-functionalized calix[8]arene ligands capable of electrocatalytically reducing CO<sub>2</sub> into different products with 2,2,2-trifluoroethanol as proton donor. The selectivity of the reaction seems to be affected by the calixarene cavity: two calixarene-free analogous complexes reduce CO<sub>2</sub> to CO almost exclusively, while the calixarene complexes produce primarily CO, H<sub>2</sub>. Interestingly, in some cases the less frequently observed CH<sub>4</sub> was also detected, albeit with low Faradaic efficiency. Thus, the manganese center placed within the calixarene cavity promotes the formation of reduced CO<sub>2</sub> products by more than two electrons and two protons, affording CH<sub>4</sub> in some cases.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2023-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202300083","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135982011","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}
Xingguang Cai, Alice Capecchi, Basak Olcay, Markus Orsi, Sacha Javor, Jean-Louis Reymond
There is an urgent need to develop new antibacterial agents against multidrug resistant bacteria. Herein we report our investigation of antimicrobial peptide dendrimers (AMPDs) active against Gram-negative bacteria, whose sequences were designed using a genetic algorithm optimizing molecular similarity to the previously reported AMPD T7 with sequence (KL)8(KKL)4(KKLL)2KKKL. Our computational approach selected analogues unlikely to emerge from a systematic study, including AMPD X66 with a non-conservative Leu→Glu mutation at the dendrimer core which proved compatible with antibacterial effects. Circular dichroism showed that this AMPD is α-helical. Molecular dynamics suggest that its α-helical structure is stabilized by an intramolecular salt bridge involving the core glutamate side chain and a lysine side chain in the dendrimer branches. More substantial variations at the dendrimer core were also tolerated such as the installation of the dianionic pegylated fatty acid side chain of the drug semaglutide potentially useful for in vivo studies.
{"title":"Exploring the Sequence Space of Antimicrobial Peptide Dendrimers","authors":"Xingguang Cai, Alice Capecchi, Basak Olcay, Markus Orsi, Sacha Javor, Jean-Louis Reymond","doi":"10.1002/ijch.202300096","DOIUrl":"10.1002/ijch.202300096","url":null,"abstract":"<p>There is an urgent need to develop new antibacterial agents against multidrug resistant bacteria. Herein we report our investigation of antimicrobial peptide dendrimers (AMPDs) active against Gram-negative bacteria, whose sequences were designed using a genetic algorithm optimizing molecular similarity to the previously reported AMPD <b>T7</b> with sequence (KL)<sub>8</sub>(<i>K</i>KL)<sub>4</sub>(<i>K</i>KLL)<sub>2</sub><i>K</i>KKL. Our computational approach selected analogues unlikely to emerge from a systematic study, including AMPD <b>X66</b> with a non-conservative Leu→Glu mutation at the dendrimer core which proved compatible with antibacterial effects. Circular dichroism showed that this AMPD is α-helical. Molecular dynamics suggest that its α-helical structure is stabilized by an intramolecular salt bridge involving the core glutamate side chain and a lysine side chain in the dendrimer branches. More substantial variations at the dendrimer core were also tolerated such as the installation of the dianionic pegylated fatty acid side chain of the drug semaglutide potentially useful for <i>in vivo</i> studies.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2023-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202300096","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135979642","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}
The Annual Wolf Prize Symposia of the Israel Chemical Society (ICS) have become a significant component of the scientific landscape of the State of Israel. These highly attended events occur annually in late May or early June as part of the Wolf Prize week, usually one day before the award ceremony in the Knesset. This account covers the one-day symposium at the Weizmann Institute of Science on June 14, 2023, the Wolf Prize ceremony in the Knesset on June 15, and several other events in Israel that week, all honoring Chuan He, Jeffrey W. Kelly, and Hiroaki Suga.
{"title":"Functions and Pathological Dysfunctions of RNA and Proteins: ICS Symposium Honoring Wolf Prize Laureates Chuan He, Jeffrey W. Kelly, and Hiroaki Suga: June 14, 2023, The Weizmann Institute of Science, Rehovot, Israel","authors":"Ehud Keinan","doi":"10.1002/ijch.202300126","DOIUrl":"10.1002/ijch.202300126","url":null,"abstract":"<p>The Annual Wolf Prize Symposia of the Israel Chemical Society (ICS) have become a significant component of the scientific landscape of the State of Israel. These highly attended events occur annually in late May or early June as part of the Wolf Prize week, usually one day before the award ceremony in the Knesset. This account covers the one-day symposium at the Weizmann Institute of Science on June 14, 2023, the Wolf Prize ceremony in the Knesset on June 15, and several other events in Israel that week, all honoring Chuan He, Jeffrey W. Kelly, and Hiroaki Suga.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2023-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41728740","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}
Despite substantial advancements in thermal and photochemical catalysis, the evolution of similar processes within the realm of organic electrochemistry has seen a slower pace. However, recent years have heralded a remarkable surge in molecular electrocatalysis. This innovative technique harnesses the power of molecular catalysts to expedite electrochemical transformations. This article underscores the application of ferrocene (Fc) as a redox catalyst in organic electrosynthesis. It delves into the extensive utilization of Fc in organic electrosynthesis, particularly emphasizing its role in the electrocatalytic generation and reactions of heteroatom- and carbon-centered radicals, among various other reactions.
{"title":"Ferrocene as a Redox Catalyst for Organic Electrosynthesis","authors":"Na Chen, Zheng-Jian Wu, Hai-Chao Xu","doi":"10.1002/ijch.202300097","DOIUrl":"10.1002/ijch.202300097","url":null,"abstract":"<p>Despite substantial advancements in thermal and photochemical catalysis, the evolution of similar processes within the realm of organic electrochemistry has seen a slower pace. However, recent years have heralded a remarkable surge in molecular electrocatalysis. This innovative technique harnesses the power of molecular catalysts to expedite electrochemical transformations. This article underscores the application of ferrocene (Fc) as a redox catalyst in organic electrosynthesis. It delves into the extensive utilization of Fc in organic electrosynthesis, particularly emphasizing its role in the electrocatalytic generation and reactions of heteroatom- and carbon-centered radicals, among various other reactions.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2023-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46528725","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}
This mini review provides an overview of a range of Ni-, Co- and Pd-catalyzed electroreductive cross-coupling reactions. The combination of homogeneous transition-metal catalysis and electrochemistry are green alternatives to traditional reductive cross-coupling reactions to form Csp2-Csp2, Csp2-Csp3 and some Csp3-Csp3 bonds in one step. Most of these reactions use the sacrificial anode process.
{"title":"Transition Metal-Catalyzed Electroreductive Cross-Couplings for C−C Bond Formation","authors":"Meng-Yu Gao, Dr. Corinne Gosmini","doi":"10.1002/ijch.202300074","DOIUrl":"10.1002/ijch.202300074","url":null,"abstract":"<p>This mini review provides an overview of a range of Ni-, Co- and Pd-catalyzed electroreductive cross-coupling reactions. The combination of homogeneous transition-metal catalysis and electrochemistry are green alternatives to traditional reductive cross-coupling reactions to form Csp<sup>2</sup>-Csp<sup>2</sup>, Csp<sup>2</sup>-Csp<sup>3</sup> and some Csp<sup>3</sup>-Csp<sup>3</sup> bonds in one step. Most of these reactions use the sacrificial anode process.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2023-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41914177","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}
Xinlong Song, Ximei Zhao, Zhongyi Zeng, Frank Rominger, Matthias Rudolph, A. Stephen K. Hashmi
A one-pot synthesis of 2-acylidene-3-oxindole and azaaurone derivatives starting from O-alkynylanilines and alkynes is presented. By means of oxidative gold catalysis the two starting materials are transferred to reactive intermediates that in situ form the target products. This double oxidation strategy enables a protecting group-free step-economic strategy towards these valuable substrate classes.
{"title":"Protecting Group-Free Gold-Catalyzed Synthesis of 2-Acylidene-3-Oxindoles and Azaaurones via a Double Oxidation Strategy","authors":"Xinlong Song, Ximei Zhao, Zhongyi Zeng, Frank Rominger, Matthias Rudolph, A. Stephen K. Hashmi","doi":"10.1002/ijch.202300094","DOIUrl":"10.1002/ijch.202300094","url":null,"abstract":"<p>A one-pot synthesis of 2-acylidene-3-oxindole and azaaurone derivatives starting from <i>O</i>-alkynylanilines and alkynes is presented. By means of oxidative gold catalysis the two starting materials are transferred to reactive intermediates that <i>in situ</i> form the target products. This double oxidation strategy enables a protecting group-free step-economic strategy towards these valuable substrate classes.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2023-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202300094","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41661197","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}
Valentine V. Courouble, Matthew D. Mann, Patrick R. Griffin
Mass spectrometry (MS) is a central analytical technique used to study proteins and biomolecules. It measures mass-to-charge ratio of ions to identify and quantify molecules in simple and complex mixtures. Technological advancement in instrumentation, sample preparation methodologies, and data analysis workflows continue to push the capabilities of MS to answer more complicated questions and vice versa. Structural proteomics uses MS-based methodologies to characterize protein structure. Specifically, but not limited to, hydrogen deuterium exchange MS (HDX-MS) and crosslinking MS (XL-MS) are complementary techniques that capture the structural plasticity inherent to proteins in solution. This review is intended to present recent progress in HDX-MS and XL-MS that have allowed these techniques to be used not only for simple recombinant protein systems but with complex cellular systems.
{"title":"Advances in Mass Spectrometry-Based Structural Proteomics: Development of HDX-MS and XL-MS Techniques from Recombinant Protein to Cellular Systems","authors":"Valentine V. Courouble, Matthew D. Mann, Patrick R. Griffin","doi":"10.1002/ijch.202300084","DOIUrl":"10.1002/ijch.202300084","url":null,"abstract":"<p>Mass spectrometry (MS) is a central analytical technique used to study proteins and biomolecules. It measures mass-to-charge ratio of ions to identify and quantify molecules in simple and complex mixtures. Technological advancement in instrumentation, sample preparation methodologies, and data analysis workflows continue to push the capabilities of MS to answer more complicated questions and vice versa. Structural proteomics uses MS-based methodologies to characterize protein structure. Specifically, but not limited to, hydrogen deuterium exchange MS (HDX-MS) and crosslinking MS (XL-MS) are complementary techniques that capture the structural plasticity inherent to proteins in solution. This review is intended to present recent progress in HDX-MS and XL-MS that have allowed these techniques to be used not only for simple recombinant protein systems but with complex cellular systems.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2023-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45857870","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}
The cover art presents Helmut Schwarz surrounded by his favorite chemistry - a collage of graphical display items selected from several papers previously published by Helmut Schwarz and his research group.