Chem最新文献_第7页

Enantioselective total syntheses of melotenine-, voacafrine-, and tabersonine-type Aspidosperma indole alkaloids

IF 23.5 1区化学

Chem Pub Date : 2025-02-25 DOI: 10.1016/j.chempr.2025.102440

Dong-Xing Tan, Jie Zhou, Cheng-Yu Gu, Ze-Yu Li, Yun-Jie Shen, Fu-She Han

{"title":"Enantioselective total syntheses of melotenine-, voacafrine-, and tabersonine-type Aspidosperma indole alkaloids","authors":"Dong-Xing Tan, Jie Zhou, Cheng-Yu Gu, Ze-Yu Li, Yun-Jie Shen, Fu-She Han","doi":"10.1016/j.chempr.2025.102440","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102440","url":null,"abstract":"Although the total synthesis of <em>aspidosperma</em> natural products has been extensively investigated, the members possessing diverse functionalities at C3 and/or C5, which display much stronger bioactivity than the non-functionalized congeners, have not been accomplished due to the structural challenges. Herein, the first catalytic asymmetric total syntheses of C11-demethoxymelotenine, 3-oxotabersonine, voacafrine I, and 3α/3β-acetonyltabersonine are presented. Our synthesis hinged on the development of an organocatalyzed desymmetric enantioselective Michael/aldol reaction of 2-(2-nitrophenyl)cyclohexane-1,3-dione for the efficient construction of a chiral [3.3.1]-bridged bicyclic scaffold and a ring opening-reorganizing tactic of the bridged bicycle for elegant construction of a 6-5-6-5-6 pentacyclic ring system bearing functionalities amenable to distinguishable elaborations at C3, C5, and C19 positions. Utilizing the strategic polycyclic core, the enantioselective total syntheses of six previously unconquered <em>aspidosperma</em>-type alkaloids and stereoisomers have been achieved via a divergent manner through appropriately manipulating the functional groups at C3, C5, and C19 at the late stage.","PeriodicalId":268,"journal":{"name":"Chem","volume":"23 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486428","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}

引用次数: 0

Desymmetrizing atroposelective bromination of N-arylcarbazoles enabled by cross-assembled bifunctional catalysts

IF 23.5 1区化学

Chem Pub Date : 2025-02-24 DOI: 10.1016/j.chempr.2025.102439

Jingxian Huang, Hui Yang, Xiao Chen, Rong Liang, Fuk-Yee Kwong, Zhifeng Huang, Ming Wah Wong, Ying-Yeung Yeung

{"title":"Desymmetrizing atroposelective bromination of N-arylcarbazoles enabled by cross-assembled bifunctional catalysts","authors":"Jingxian Huang, Hui Yang, Xiao Chen, Rong Liang, Fuk-Yee Kwong, Zhifeng Huang, Ming Wah Wong, Ying-Yeung Yeung","doi":"10.1016/j.chempr.2025.102439","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102439","url":null,"abstract":"Asymmetric catalytic halofunctionalization has gained prominence for introducing carbon point chirality and halogen functionality simultaneously. Axially chiral biaryls possess a range of promising applications; however, their synthesis through asymmetric halogenation is limited. Here, we report the synthesis of C–N axially chiral <em>N</em>-arylcarbazoles through desymmetrizing atroposelective bromination. This process is facilitated by a catalyst blend consisting of a chiral phosphoric acid and an achiral Lewis base. The resulting bromo-carbazoles contain readily modifiable halogen handles, allowing for the introduction of additional chiral axes through diastereoselective cross-coupling. These axially chiral compounds exhibit high fluorescence quantum yields and satisfactory circularly polarized luminescence performance. Mechanistic studies indicate that the chiral phosphate and achiral pyridine catalysts cross-assemble through C–H nonclassical hydrogen bonds and C–X halogen bonds, creating a confined microenvironment for efficient enantiofacial discrimination of substrates. This research paves the way for an approach to synthesizing mimics of planar chiral arenes for applications in materials science.","PeriodicalId":268,"journal":{"name":"Chem","volume":"2 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477530","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}

引用次数: 0

Dicobalt-catalyzed N=N coupling reactions of tertiary alkyl azides to form azoalkanes

IF 23.5 1区化学

Chem Pub Date : 2025-02-24 DOI: 10.1016/j.chempr.2025.102437

Kyle B. Brook, Sumeet R. Sahoo, Christopher Uyeda

引用次数: 0

Ribosomal pentapeptide nitration for non-ribosomal peptide antibiotic precursor biosynthesis

IF 23.5 1区化学

Chem Pub Date : 2025-02-20 DOI: 10.1016/j.chempr.2025.102438

Leo Padva, Lukas Zimmer, Jemma Gullick, Yongwei Zhao, Vishnu Mini Sasi, Ralf B. Schittenhelm, Colin J. Jackson, Max J. Cryle, Max Crüsemann

{"title":"Ribosomal pentapeptide nitration for non-ribosomal peptide antibiotic precursor biosynthesis","authors":"Leo Padva, Lukas Zimmer, Jemma Gullick, Yongwei Zhao, Vishnu Mini Sasi, Ralf B. Schittenhelm, Colin J. Jackson, Max J. Cryle, Max Crüsemann","doi":"10.1016/j.chempr.2025.102438","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102438","url":null,"abstract":"Peptide natural products possess a fascinating array of complex structures and diverse biological activities. Central to this is a repertoire of structurally modified amino acid building blocks, which stem from fundamentally different biosynthetic pathways for peptides of non-ribosomal and ribosomal origins. Given these origins, the integration of non-ribosomal and ribosomal peptide biosynthesis has previously been thought implausible. Now, we report how nature has synergized ribosomal and non-ribosomal peptide pathways in the biosynthesis of the rufomycins, exceptionally potent antitubercular antibiotics. In this pathway, a biarylitide-type ribosomal pentapeptide precursor is nitrated by a modified cytochrome P450 biaryl-crosslinking enzyme. The nitrated residue, key for antibiotic activity, is liberated by a dedicated protease before activation and peptide incorporation by the non-ribosomal rufomycin synthetase assembly line. This resolves the enigmatic origins of 3-nitrotyrosine within rufomycin biosynthesis and unveils a novel function for ribosomally synthesized peptides as templates for biosynthesis of modified non-ribosomal peptide building blocks.","PeriodicalId":268,"journal":{"name":"Chem","volume":"15 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452171","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}

引用次数: 0

Organic-solvent-free primary solvation shell for low-temperature aqueous zinc batteries 用于低温水溶锌电池的无有机溶剂一次溶壳

IF 19.1 1区化学

Chem Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.09.001

Lishan Geng , Jiashen Meng , Xuanpeng Wang , Weidong Wu , Kang Han , Meng Huang , Chunhua Han , Lu Wu , Jinghao Li , Liang Zhou , Liqiang Mai

{"title":"Organic-solvent-free primary solvation shell for low-temperature aqueous zinc batteries","authors":"Lishan Geng , Jiashen Meng , Xuanpeng Wang , Weidong Wu , Kang Han , Meng Huang , Chunhua Han , Lu Wu , Jinghao Li , Liang Zhou , Liqiang Mai","doi":"10.1016/j.chempr.2024.09.001","DOIUrl":"10.1016/j.chempr.2024.09.001","url":null,"abstract":"<div><div>Conventional hybrid aqueous electrolytes with solvated organic co-solvents encounter sluggish desolvation kinetics, especially under low-temperature conditions, due to the strong binding of organic solvents with Zn<sup>2+</sup>. Here, we develop a class of hybrid aqueous electrolytes with an organic-solvent-free primary solvation shell, favoring facile desolvation. As demonstrated by 1 M zinc acetate with dimethyl sulfoxide (DMSO) dipolar aprotic solvent, CH<sub>3</sub>COO<sup>−</sup> and H<sub>2</sub>O surround Zn<sup>2+</sup>, forming Zn<sup>2+</sup>(CH<sub>3</sub>COO<sup>−</sup>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub> clusters. The enhanced hydrogen bonds between solvated CH<sub>3</sub>COO<sup>−</sup> and H<sub>2</sub>O hinder DMSO from replacing solvated H<sub>2</sub>O. This weak solvation structure facilitates fast charge transfer kinetics and rapid Zn<sup>2+</sup> flow through gradient solid electrolyte interphase. At −20°C, stable plating/stripping (5,600 h) and high Zn utilization (51%) are achieved. Furthermore, polyaniline||Zn batteries manifest low polarization (0.05 V), long cycling (8,800 cycles), and high rate. Importantly, this design strategy is generally extended to other hybrid electrolyte systems. This work represents advancements in electrolyte design for aqueous batteries.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102302"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142363118","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}

引用次数: 0

Engineering biotic-abiotic hybrid systems for solar-to-chemical conversion 太阳能-化学转换的生物-生物混合系统工程

IF 19.1 1区化学

Chem Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.10.018

Wentao Song , Xinyue Zhang , Wanrong Li , Bowen Li , Bin Liu

{"title":"Engineering biotic-abiotic hybrid systems for solar-to-chemical conversion","authors":"Wentao Song , Xinyue Zhang , Wanrong Li , Bowen Li , Bin Liu","doi":"10.1016/j.chempr.2024.10.018","DOIUrl":"10.1016/j.chempr.2024.10.018","url":null,"abstract":"<div><div>Constructing biotic-abiotic hybrid systems for solar energy conversion receives growing interest owing to their sustainable and eco-friendly approach to producing chemicals. The integration of intracellular biochemical pathways with semiconductor materials offers superior product selectivity and efficient light utilization in solar-driven biocatalysis. However, the complicated multidisciplinary features and limited understanding of extracellular electron transfer at the biological-material interfaces hinder the practical application of biotic-abiotic hybrid systems for converting solar energy. In this perspective, we summarize the fundamental mechanisms of biohybrid systems for solar-to-chemical conversion and highlight ongoing challenges and promising directions for future development. First, a comprehensive overview of biotic-abiotic hybrid systems is introduced together with the mechanism of extracellular electron transfer for chemical production. Then, recent achievements of biohybrid systems for H<sub>2</sub> production, CO<sub>2</sub> reduction, N<sub>2</sub> fixation, and chemical synthesis are discussed in detail. Finally, the current challenges in biotic-abiotic hybrid systems and prospective research directions are explored.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102351"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673764","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}

引用次数: 0

DNA-enzyme nanostructures enhance enzyme stability and functionality DNA 酶纳米结构可增强酶的稳定性和功能性

IF 19.1 1区化学

Chem Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2025.102451

Seungheon Lee , Devleena Samanta

引用次数: 0

Non-covalent assembly of chiral Archimedean polyhedra

IF 19.1 1区化学

Chem Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2025.102449

Honghao Cao , Hanyang Shen , Zhijie Chen

引用次数: 0

Engineering a photoenzyme to use red light 利用红光改造光酵素

IF 19.1 1区化学

Chem Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.09.017

Jose M. Carceller , Bhumika Jayee , Claire G. Page , Daniel G. Oblinsky , Gustavo Mondragón-Solórzano , Nithin Chintala , Jingzhe Cao , Zayed Alassad , Zheyu Zhang , Nathaniel White , Danny J. Diaz , Andrew D. Ellington , Gregory D. Scholes , Sijia S. Dong , Todd K. Hyster

{"title":"Engineering a photoenzyme to use red light","authors":"Jose M. Carceller , Bhumika Jayee , Claire G. Page , Daniel G. Oblinsky , Gustavo Mondragón-Solórzano , Nithin Chintala , Jingzhe Cao , Zayed Alassad , Zheyu Zhang , Nathaniel White , Danny J. Diaz , Andrew D. Ellington , Gregory D. Scholes , Sijia S. Dong , Todd K. Hyster","doi":"10.1016/j.chempr.2024.09.017","DOIUrl":"10.1016/j.chempr.2024.09.017","url":null,"abstract":"<div><div>Photoenzymatic reactions involving flavin-dependent “ene”-reductases (EREDs) rely on protein-templated charge transfer (CT) complexes between the cofactor and substrate for radical initiation. These complexes typically absorb in the blue region of the electromagnetic spectrum. Here, we engineered an ERED to form CT complexes that absorb red light. Mechanistic studies indicate that red-light activity is due to the growth of a red-absorbing shoulder off the previously identified cyan absorption feature. Molecular dynamics simulations, docking, and excited-state calculations suggest that the cyan feature involves a π→π∗ transition on flavin, whereas the red-light absorption is a π→π∗ transition between flavin and the substrate. Differences in the electronic transition are due to changes in the substrate-binding conformation and allosteric tuning of the electronic structure of the cofactor-substrate complex. Microenvironment tuning of the CT complex for red-light activity is observed with other engineered photoenzymatic reactions, highlighting this effect’s generality.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102318"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439790","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}

引用次数: 0

Field-enhanced CO electroreduction in membrane electrolyzers at a dehydrated interface 脱水界面膜电解槽中的场增强型一氧化碳电还原

IF 19.1 1区化学

Chem Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.10.019

Wenhao Ren , Huanlei Zhang , Miyeon Chang , Nanjun Chen , Wenchao Ma , Jun Gu , Meng Lin , Xile Hu

引用次数: 0