Israel Journal of Chemistry最新文献

{"title":"Π-acid catalysis – challenges, advances, and opportunities","authors":"Dr. Yuri Tulchinsky, Prof. Ehud Keinan","doi":"10.1002/ijch.202300132","DOIUrl":"https://doi.org/10.1002/ijch.202300132","url":null,"abstract":"<p>Π-acid catalysis is one of the last two decades′ most exciting developments in synthetic organic chemistry. Because of the mild conditions employed and high functional group tolerance, π-acid catalysis became a tool of choice for the selective activation of double and triple C−C bonds at the late stages of multistep syntheses. At the same time, owing to the simplicity of the reaction setup, it also provides an easy and atom-economic route towards a broad array of valuable precursors.</p><p>Traditionally, the field of π-acid catalysis has relied on complexes of Au(I) and Pt(II). These electron-rich cations are well-suited for the carbophilic activation of C−C multiple bonds. On the one hand, they are highly polarizable and hence can efficiently interact with the <i>η</i><sub>2</sub>-coordinated “soft” alkene or alkyne ligands. Yet, on the other hand, they are sufficiently electrophilic to render those ligands susceptible to nucleophilic attacks. While gold and platinum still maintain their privileged position in π-acid catalysis, the growing list of metals employable as π-acid catalysts now includes not only other noble elements (Pd, Rh, etc.), but also some earth-abundant ones, such as Cu, Zn, and even Al, providing cheaper alternatives for the precious metals.</p><p>The choice of ancillary ligands plays a crucial role in imparting an electrophilic character on metal centers for use as π-acid catalysts. New strong electron-withdrawing ancillary ligands were developed in search of better catalysts. A possible way to achieve this goal is by increasing the π-acidity of moderately π-acidic ligands, such as tertiary phosphines and N-heterocyclic carbenes (NHCs). In the present issue, two contributions - a communication by Manuel Alcarazo and a research article by Fumitoshi Shibahara - represent this endeavor.</p><p>Prof. Alcarazo is renowned for introducing the α-cationic phosphines and arsines as a novel class of highly π-acidic ancillary ligands for catalysis, mostly in Au(I) and Pt(II) systems. In recent years, his group has been active in developing asymmetric π-acid catalysis with chiral α-cationic phosphinates. A short communication presented in this issue describes the application of these unusual ancillary ligands for a highly enantioselective one-pot preparation of chiral <i>C<sub>2</sub></i>-symmetric [5]helicenes with two peripheral axial stereogenic centers. Asymmetric π-acid catalysis by Au(I) and Au(III) complexes is thoroughly addressed in a comprehensive review by Nitin Patil. Surprisingly, despite the prominent role of Au in π-acid catalysis in general, chiral gold catalysts have received much less attention. Prof. Patil's review aims at filling in this lacune and provides a retrospect of the significant developments in this area during the last 15 years.</p><p>A research article by Prof. Shibahara presents a different kind of π-acidic ancillary ligands. His group reports on a novel series of fused NHC ligands with electron-withdra","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"63 9","pages":""},"PeriodicalIF":3.2,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202300132","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50130822","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":"Recent Applications of Paired Electrolysis in Organic Synthesis","authors":"Ke-Jin Jiao,&nbsp;Xiao-Tong Gao,&nbsp;Cong Ma,&nbsp;Ping Fang,&nbsp;Tian-Sheng Mei","doi":"10.1002/ijch.202300085","DOIUrl":"10.1002/ijch.202300085","url":null,"abstract":"<p>Recent years have witnessed a renaissance of organic electrochemistry since the cheap, safe, sustainable electron could be employed as a traceless redox agent to facilitate redox conversions. Additionally, divergent selectivity could be achieved by tuning the potential or current of the electrochemical reaction. Compared to electrooxidation or electroreduction reactions, paired electrolysis represents a more practical and energy-efficient strategy that delivers the products by making use of both anodic and cathodic reactions simultaneously. This mini-review summarized the breakthroughs and recent advances in this fascinating field and mainly is divided into three parts: parallel, sequential, and convergent paired electrolysis.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"64 1-2","pages":""},"PeriodicalIF":3.2,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135536604","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}

{"title":"Cover Picture: (Isr. J. Chem. 9/2023)","authors":"","doi":"10.1002/ijch.202380901","DOIUrl":"https://doi.org/10.1002/ijch.202380901","url":null,"abstract":"<p>The cover picture illustrates symbolically the critical step in π-acid catalysis as a bullfighting scene: a metal catalyst (the toreador) binds an alkyne and activates it for an attack by a nucleophile (the bull). Cover image by Dr. Igor Armiach.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"63 9","pages":""},"PeriodicalIF":3.2,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202380901","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"50155092","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":"Electrochemical C7-Indole Alkenylation via Rhodium Catalysis","authors":"Agnese Zangarelli,&nbsp;Binbin Yuan,&nbsp;Prof. Dr. Lutz Ackermann","doi":"10.1002/ijch.202300103","DOIUrl":"10.1002/ijch.202300103","url":null,"abstract":"<p>Indole derivatives are fundamental structural units in many bioactive compounds and molecular materials. The site-selective C7-functionalization of these moieties has been proven to be extremely challenging due to the inherent reactivity of the C2- and C3-positions. Herein, we report the first electro-C7-alkenylation of indoles. This novel and sustainable methodology provides highly exclusive access to the C7-position devoid of often toxic and expensive chemical oxidants. Moreover, an array of substrates was successfully alkenylated at the C7-position, and versatile product diversification was achieved.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"64 1-2","pages":""},"PeriodicalIF":3.2,"publicationDate":"2023-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202300103","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135816172","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":"Chemoenzymatic Tagging of Tn/TF/STF Antigens in Living Systems","authors":"Yi Yang,&nbsp;Mingkuan Chen,&nbsp;Mengyao Wu,&nbsp;Senlian Hong,&nbsp;Bing Gao,&nbsp;Yonghui Liu,&nbsp;Chenhua Yu,&nbsp;Travis S. Young,&nbsp;Digantkumar Gopaldas Chapla,&nbsp;Jeong-Yeh Yang,&nbsp;John R. Cappiello,&nbsp;Jie P. Li,&nbsp;K. Barry Sharpless,&nbsp;Kelley W. Moremen,&nbsp;Peng Wu","doi":"10.1002/ijch.202300081","DOIUrl":"10.1002/ijch.202300081","url":null,"abstract":"<p>Truncated mucin-type O-glycans, such as Tn-associated antigens, are aberrantly expressed biomarkers of cancer, but remain challenging to target. Reactive antibodies to these antigens either lack high affinity or are prone to antigen escape. Here, we have developed a robust chemoenzymatic strategy for the global labeling of Tn-associated antigens, i. e. Tn (GalNAcα-O-Ser/Thr), Thomsen-Friedenreich (Galβ1-3GalNAcα-O-Ser/Thr, TF) and STF (Neu5Acα2-3Galβ1-3GalNAcα-O-Ser/Thr, STF) antigens, in human whole blood with high efficiency and selectivity. This method relies on the use of the O-glycan sialyltransferase ST6GalNAc1 to transfer a sialic acid-functionalized adaptor to the GalNAc residue of these antigens. By tagging, the adaptor functionalized antigens can be easily targeted by customized strategies such as, but not limited to, chimeric antigen receptor T-Cells (CAR-T). We expect this tagging system to find broad applications in cancer diagnostics and targeting in combination with established strategies.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"63 10-11","pages":""},"PeriodicalIF":3.2,"publicationDate":"2023-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ijch.202300081","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135395547","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":"Mechanochemical difluoromethylation of (thio)phenols and N-heterocycles","authors":"Joseph Ford,&nbsp;Benjamin Hopkin,&nbsp;Jeroen B. I. Sap,&nbsp;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":"63 10-11","pages":""},"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}

{"title":"Calix[8]arene-Based Manganese Complexes for Electrocatalytic CO2 Reduction","authors":"Armando Berlanga-Vázquez,&nbsp;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 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.</p>","PeriodicalId":14686,"journal":{"name":"Israel Journal of Chemistry","volume":"64 6-7","pages":""},"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}

{"title":"Exploring the Sequence Space of Antimicrobial Peptide Dendrimers","authors":"Xingguang Cai,&nbsp;Alice Capecchi,&nbsp;Basak Olcay,&nbsp;Markus Orsi,&nbsp;Sacha Javor,&nbsp;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)₈(<i>K</i>KL)₄(<i>K</i>KLL)₂<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":"63 10-11","pages":""},"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}

{"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":"63 9","pages":""},"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}

{"title":"Ferrocene as a Redox Catalyst for Organic Electrosynthesis","authors":"Na Chen,&nbsp;Zheng-Jian Wu,&nbsp;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":"64 1-2","pages":""},"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}