ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.09.014
Nicholas D. Chiappini
{"title":"Arylative difunctionalization of olefins using easily accessed organobismuth (V) reagents","authors":"Nicholas D. Chiappini","doi":"10.1016/j.chempr.2024.09.014","DOIUrl":"10.1016/j.chempr.2024.09.014","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Li and Rawal present an exciting new application of Ar<sub>3</sub>BiCl<sub>2</sub> as convenient reagents for arylative difunctionalization of alkenes using visible or near-visible light. Unburdened by air and moisture sensitivity, the method affords rapid and facile azido-, cyano-, and chloro-arylation of a bevy of functionalized alkenes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 2945-2947"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.09.012
Chenxin Ou , Jinze Lv , Aaron J. Lim , Qing-Hui Guo , Yuanning Feng
{"title":"A light-driven chloride anion transporter","authors":"Chenxin Ou , Jinze Lv , Aaron J. Lim , Qing-Hui Guo , Yuanning Feng","doi":"10.1016/j.chempr.2024.09.012","DOIUrl":"10.1016/j.chempr.2024.09.012","url":null,"abstract":"<div><div>Recent advances in artificial transmembrane transporters that may address the limitations of natural ion channels include a photoswitchable Cl<sup>−</sup> anion pump developed by Aprahamian et al., reported in <em>Science</em>,<span><span><sup>1</sup></span></span> utilizing hydrazone units for active transport against the concentration gradient. This molecular transporter leverages light-induced isomerization to control anion grabbing and releasing, showing significant potential for drug discovery and molecular machinery.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 2940-2942"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.05.021
{"title":"Modifying commodity-relevant unsaturated polymers via Co-catalyzed MHAT","authors":"","doi":"10.1016/j.chempr.2024.05.021","DOIUrl":"10.1016/j.chempr.2024.05.021","url":null,"abstract":"<div><div><span>The past 2 decades have witnessed the rapid development of CoSalen-catalyzed hydrofunctionalization reactions, mostly on terminal and conjugation-activated olefins. However, the use of 1,2-dialkyl-substituted alkenes continues to pose challenges. In this study, we revisit this substrate class in the context of Carreira-type hydrofunctionalization reactions and introduce a simple yet effective modification (over a 250-fold-increase in </span>turnover number<span><span> [TON]). Near-quantitative yields can be achieved at a low catalyst loading, typically 0.05 mol %. The key lies in inhibiting the degradation of the salen<span> backbone using molecular sieves<span>. This protocol facilitates a study on the metal hydride </span></span></span>hydrogen atom<span><span> transfer (MHAT) regioselectivity of this type of alkene. We found that allylic electron-negative groups and </span>hyperconjugation have profound effects, yielding regioisomeric ratios ranging from 6.5:1 to < 1:20. The high TONs, mild conditions, and versatility of this method further enable its application in the post-polymerization modification of several olefin-rich, commodity-relevant polymers, demonstrating the rich potential of MHAT hydrofunctionalization in macromolecular settings.</span></span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3088-3099"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.08.009
Jing Li , Haohong Duan
{"title":"Recent progress in energy-saving hydrogen production by coupling with value-added anodic reactions","authors":"Jing Li , Haohong Duan","doi":"10.1016/j.chempr.2024.08.009","DOIUrl":"10.1016/j.chempr.2024.08.009","url":null,"abstract":"<div><div>Replacement of the oxygen evolution reaction (OER) by energetically more favorable electrooxidation reactions opens up an innovative pathway for energy-saving hydrogen (H<sub>2</sub>) production. In particular, the electrooxidation of biomass molecules, plastic wastes, and organic compounds has attracted escalating interest in recent years, owing to its potential for simultaneous H<sub>2</sub> production at the cathode and value-added chemical and fuel generation at the anode. This review article does not aim to provide a comprehensive overview of these reactions but rather to highlight the key advancements in the strategies of reaction design, activity enhancement, and selectivity regulation based on the features and challenges in each type of reaction. Through this review of key advancements, we offer mechanistic insights that guide the design of more efficient coupling systems. Lastly, the challenges and future prospects in this field are discussed.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3008-3039"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.07.008
Zhongbo Zhang , Dániel Csókás , Israel Fernández , Mihaiela C. Stuparu
{"title":"Chiral stacks of a curved nanographene","authors":"Zhongbo Zhang , Dániel Csókás , Israel Fernández , Mihaiela C. Stuparu","doi":"10.1016/j.chempr.2024.07.008","DOIUrl":"10.1016/j.chempr.2024.07.008","url":null,"abstract":"<div><div>Despite enormous advances in the edge extension chemistry of nanographenes, examples of <em>peri</em>-annulations and the knowledge of their effect on molecular properties remain scarce. Here, we show the synthesis of a curved C<sub>60</sub>S<sub>5</sub> nanographene comprising quintuple [5]thiahelicenes arranged in a <em>C</em><sub>5</sub>-symmetric fashion on the zigzag edge (<em>L</em>-region) of a bowl-shaped corannulene core. The synthesis is achieved with the help of Stille coupling, alkynyl thiolation, sulfide/aryne cyclization, and direct arylation reactions. The prepared bowl-helix chiral structure absorbs and emits in the visible and near-IR regions. It assembles into persistent molecular bilayer graphene stacks in solution, solid state, and gas phase. The concave cavities of the supramolecular dimers can recognize the convex surfaces of fullerene C<sub>60</sub> through shape complementarity and π-π stacking interactions in the solid state. A properties comparison with <em>ortho</em>-annulated analogs and archetypical nanographenes indicates the superiority of <em>peri</em>-annulations in the design of molecular graphenes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3199-3211"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141918669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.07.036
Li Li , Viresh H. Rawal
{"title":"Transition metal-free difunctionalization of unactivated alkenes: Arylation/azidation, arylation/chlorination, and arylation/cyanation","authors":"Li Li , Viresh H. Rawal","doi":"10.1016/j.chempr.2024.07.036","DOIUrl":"10.1016/j.chempr.2024.07.036","url":null,"abstract":"<div><div>Arylethylamines represent a privileged scaffold in pharmaceutical compounds and form the backbone of many medical drugs, including those used for treating neurological diseases and pain. Their biomedical significance has inspired new synthetic methods that rely on transition metal-catalyzed aminoarylation reaction to an alkene, often in conjunction with a photoredox catalyst or a photosensitizer and guided by a directing or stabilizing group. Here, we introduce a simple and effective method for the azidoarylation of unactivated alkenes under transition metal-free conditions. Visible- or near-UV-light irradiation of readily available triarylbismuth dichlorides generates an aryl radical that selectively adds to the alkene, and the resulting homobenzyl radical is intercepted by an amine equivalent. This method offers a broad substrate scope and also enables the arylchlorination and arylcyanation of unactivated alkenes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3243-3253"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142118203","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.07.026
Florian Hubrich , Sanath K. Kandy , Clara Chepkirui , Chandrashekhar Padhi , Silja Mordhorst , Philipp Moosmann , Tao Zhu , Muriel Gugger , Jonathan R. Chekan , Jörn Piel
{"title":"Ribosomal peptides with polycyclic isoprenoid moieties","authors":"Florian Hubrich , Sanath K. Kandy , Clara Chepkirui , Chandrashekhar Padhi , Silja Mordhorst , Philipp Moosmann , Tao Zhu , Muriel Gugger , Jonathan R. Chekan , Jörn Piel","doi":"10.1016/j.chempr.2024.07.026","DOIUrl":"10.1016/j.chempr.2024.07.026","url":null,"abstract":"<div><div>Isoprenoid modifications of proteins and peptides serve fundamental biological functions and are of therapeutic interest. While C<sub>15</sub> (farnesyl) and C<sub>20</sub> (geranylgeranyl) moieties are prevalent among proteins, known ribosomal peptide prenylations involve shorter-chain units not exceeding farnesyl in size. To our knowledge, cyclized terpene moieties have not been reported from either biomolecule class. Here, we used targeted genome mining and heterologous pathway reconstitution to identify ribosomally synthesized and post-translationally modified peptides (RiPPs) with elaborate, cyclized geranylgeranyl modifications. The installing maturases commonly feature fused prenyltransferase-terpene cyclase architectures. We characterized two bifunctional maturases with distinct prenyltransferase folds and identified the terminal product of a cyanobacterial proteusin as an exceptionally complex pseudosteroid-annelated polycyclic peptide. Bioassays suggest modest anti-cyanobacterial activity with the modification being crucial for activity. Genome data predict cyclic isoprenoid units for various RiPP families, including proteusin, Nif11, and lasso peptides, and thus the broader natural and biotechnological compatibility of the maturase system.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3224-3242"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142142934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.05.022
{"title":"Hierarchical porous covalent organic framework nanosheets with adjustable large mesopores","authors":"","doi":"10.1016/j.chempr.2024.05.022","DOIUrl":"10.1016/j.chempr.2024.05.022","url":null,"abstract":"<div><div><span>Synchronous manipulation of meso-structure and architecture of covalent organic frameworks<span><span><span> (COFs) is vital for customized applications but still remains challenging. Here, we develop a polymerization-induced co-assembly approach to construct hierarchical porous COF-based </span>nanosheets with adjustable large </span>mesopores (7–40 nm), intrinsic micropores (∼1.2 nm), ultra-thin thickness (∼24 nm), and a crystalline wall. Furthermore, density functional theory calculations and adsorption experiments indicated that the complementarity of the two-dimensional architecture and intrinsic micropores of COFs can effectively confine iodine molecules. Meanwhile, the exposed nitrogen-containing active sites created by the unique mesoporous structure can strongly anchor iodine species, thereby greatly inhibiting their dissolution and shuttling. Therefore, as a cathode for zinc-iodine battery, they delivered an outstanding rate capability (191.2 mAh g</span></span><sup>−1</sup> at 0.5 A g<sup>−1</sup>) and stable long-term cyclability (154.8 mAh g<sup>−1</sup> at 3 A g<sup>−1</sup> after 20,000 cycles). This approach sheds light on the precise fabrication of crystalline porous materials for diverse applications.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3100-3113"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.05.024
{"title":"Terpenoid-based high-performance polyester with tacticity-independent crystallinity and chemical circularity","authors":"","doi":"10.1016/j.chempr.2024.05.024","DOIUrl":"10.1016/j.chempr.2024.05.024","url":null,"abstract":"<div><div>The development of chemically circular, bio-based polymers is an urgently needed solution to combat the plastic waste crisis. However, the most prominent, commercially implemented bio-based aliphatic polyester, poly(lactic acid) (PLA), is brittle, therefore largely limiting its broad applications. Herein, we introduce a class of aliphatic polyesters produced through the ring-opening polymerization (ROP) of (1<em>R</em>,5<em>S</em>)-8,8-dimethyl-3-oxabicyclo[3.2.1]octan-2-one (D-CamL) and the racemic mixture (<em>rac</em>-CamL), which exhibit superior material properties relative to PLA. A metal-based or organic catalyst was used for the modulation of polymer tacticity. Notably, regardless of tacticity, poly(CamL) exhibits intrinsic crystallinity, resulting in polyesters with high yield stress (24–39 MPa), high Young’s modulus (1.36–2.00 GPa), tunable fracture strains (6%–218%), and high melting temperatures (161°C–225°C). Importantly, poly(CamL) can be chemically recycled to monomer in high yield, and virgin-quality poly(CamL) is obtained after repolymerization. Overall, poly(CamL) represents a new class of bio-derived and chemically circular high-performance polyesters.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 3040-3054"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPub Date : 2024-10-10DOI: 10.1016/j.chempr.2024.09.003
Tao Tu , Yong-Gui Zhou , Yong Tang , Boliang Lou , Shu-Li You
{"title":"The legacy of Professor Li-Xin Dai: Organometallic and asymmetric catalysis","authors":"Tao Tu , Yong-Gui Zhou , Yong Tang , Boliang Lou , Shu-Li You","doi":"10.1016/j.chempr.2024.09.003","DOIUrl":"10.1016/j.chempr.2024.09.003","url":null,"abstract":"<div><div>Prof. Li-Xin Dai will always be remembered for his development of organometallic chemistry and asymmetric synthesis, especially for the refining and synthesis of aureomycin, organoboron chemistry, and the development of novel chiral ligands for transition-metal-catalyzed asymmetric reactions. In addition to making significant contributions to science, Prof. Dai has also made a profound impact as an esteemed educator and mentor, imparting his knowledge and work ethic to future generations of chemists and fostering fruitful collaborations with his colleagues.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 10","pages":"Pages 2953-2962"},"PeriodicalIF":19.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}