Nature chemistry最新文献_第9页

Stereoselective alkylation of saturated heterocycles 饱和杂环的立体选择性烷基化。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-28 DOI: 10.1038/s41557-025-01754-7

Yan Li, Xi Lu

引用次数: 0

Flexible interaction patches lead to building blocks with fluctuating valency 灵活的交互补丁导致构建块具有波动的价

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-27 DOI: 10.1038/s41557-025-01756-5

Tine C. M. Stevens, Pepijn G. Moerman

引用次数: 0

A glycan foldamer that uses carbohydrate-aromatic interactions to perform catalysis. 一种利用碳水化合物-芳香相互作用进行催化作用的聚糖折叠物。

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-26 DOI: 10.1038/s41557-025-01763-6

Kaimeng Liu, Martina Delbianco

{"title":"A glycan foldamer that uses carbohydrate-aromatic interactions to perform catalysis.","authors":"Kaimeng Liu, Martina Delbianco","doi":"10.1038/s41557-025-01763-6","DOIUrl":"10.1038/s41557-025-01763-6","url":null,"abstract":"In nature, the ability to catalyse reactions is primarily associated with proteins and ribozymes. Inspired by these systems, peptide-based catalysts have been designed to accelerate chemical reactions and/or ensure regio- and stereoselective transformations. We wondered whether other biomolecules (such as glycans) could be designed to perform catalytic functions, expanding the portfolio of synthetic functional oligomers. Here we report a glycan foldamer inspired by the natural Sialyl Lewis X antigen that acts as catalyst in a chemical reaction. This glycan-based catalyst benefits from structural rigidity and modular adaptability, incorporating a substrate-recognition motif alongside a catalytic active site. Leveraging the inherent ability of carbohydrates to engage in CH-π interactions with aromatic substrates, we demonstrate the recruitment and functionalization of a tryptophan via a Pictet-Spengler transformation. Our modular glycan catalyst accelerates the reaction kinetics, enabling the modification of tryptophan-containing peptides in aqueous environments. Our findings pave the way for the development of glycan-based catalysts and suggest the possibility of catalytic capabilities of glycans in biological contexts.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":19.2,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143516250","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}

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Enantioselective photocatalytic synthesis of bicyclo[2.1.1]hexanes as ortho-disubstituted benzene bioisosteres with improved biological activity 对映选择性光催化合成邻二取代苯生物同位酯[2.1.1

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-02-25 DOI: 10.1038/s41557-025-01746-7

Pablo Garrido-García, Irene Quirós, Paula Milán-Rois, Silvia Ortega-Gutiérrez, Mar Martín-Fontecha, Luis A. Campos, Álvaro Somoza, Israel Fernández, Thomas Rigotti, Mariola Tortosa

{"title":"Enantioselective photocatalytic synthesis of bicyclo[2.1.1]hexanes as ortho-disubstituted benzene bioisosteres with improved biological activity","authors":"Pablo Garrido-García, Irene Quirós, Paula Milán-Rois, Silvia Ortega-Gutiérrez, Mar Martín-Fontecha, Luis A. Campos, Álvaro Somoza, Israel Fernández, Thomas Rigotti, Mariola Tortosa","doi":"10.1038/s41557-025-01746-7","DOIUrl":"https://doi.org/10.1038/s41557-025-01746-7","url":null,"abstract":"1,5-Disubstituted bicyclo[2.1.1]hexanes are bridged scaffolds with well-defined exit vectors that are becoming increasingly popular building blocks in medicinal chemistry because they are saturated bioisosteres of ortho-substituted phenyl rings. Here we have developed a Lewis-acid-catalysed [2 + 2] photocycloaddition to obtain these motifs as enantioenriched scaffolds, providing an efficient approach for their incorporation in a variety of drug analogues. Retention of the biological activity of the bicyclo[2.1.1]hexane-containing analogues in the specific proteins targeted by the original drugs has confirmed the suitability of this moiety to serve as a bioisostere of ortho-substituted phenyl rings. Moreover, we have studied the potential of the different enantiomers of the drug analogues to selectively induce cytotoxicity in a panel of tumour cell lines, observing markedly differential effects for the two enantiomers and a substantial improvement over the corresponding sp2-based drugs. This showcases that the control of the absolute configuration and tridimensionality of the drug analogue has a large impact on its biological properties.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143485626","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

Photomediated aliphatic C–H functionalization 脂族C-H功能化

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-24 DOI: 10.1038/s41557-025-01755-6

Tin V. T. Nguyen, Jerome Waser

引用次数: 0

Hydrogen transfer pathway controls selectivity in electrocatalytic CO2 reduction 氢转移途径控制电催化CO2还原的选择性

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-24 DOI: 10.1038/s41557-025-01761-8

Chengzhang Wan, Joel W. Ager, Yu Huang

引用次数: 0

Light-activated hypervalent iodine agents enable diverse aliphatic C–H functionalization 光活化的高价碘剂使多种脂肪C-H功能化

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-24 DOI: 10.1038/s41557-025-01749-4

Zhipeng Lu, John Putziger, Song Lin

{"title":"Light-activated hypervalent iodine agents enable diverse aliphatic C–H functionalization","authors":"Zhipeng Lu, John Putziger, Song Lin","doi":"10.1038/s41557-025-01749-4","DOIUrl":"10.1038/s41557-025-01749-4","url":null,"abstract":"The functionalization of aliphatic C–H bonds is a crucial step in the synthesis and transformation of complex molecules relevant to medicinal, agricultural and materials chemistry. As such, there is substantial interest in the development of general synthetic platforms that enable the efficient diversification of aliphatic C–H bonds. Here we report a hypervalent iodine reagent that releases a potent hydrogen atom abstractor for C–H activation under mild photochemical conditions. Using this reagent, we demonstrate selective (N-phenyltetrazole)thiolation of aliphatic C–H bonds for a broad scope of substrates. The synthetic utility of the thiolated products is showcased through various derivatizations. Simply by altering the radical trapping agent, our method can directly transform C–H bonds into diverse functionalities, including C–S, C–Cl, C–Br, C–I, C–O, C–N, C–C and C=C bonds. Aliphatic C–H functionalization is a valuable tool in organic synthesis. Now a hypervalent iodine reagent has been shown to release a potent hydrogen atom abstractor for C–H activation under mild photochemical conditions. This enables the transformation of C–H bonds into diverse functional groups with tunable control over the site selectivity.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 3","pages":"365-372"},"PeriodicalIF":19.2,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477399","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

A programmable biomimetic cytoskeleton 一个可编程的仿生细胞骨架

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-24 DOI: 10.1038/s41557-025-01757-4

Henrike Niederholtmeyer

引用次数: 0

Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols 生物衍生二元醇无受体脱氢聚合生成的聚乙烯类材料的催化闭环循环利用

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-21 DOI: 10.1038/s41557-025-01753-8

Xin Liu, Zhitao Hu, Emma M. Rettner, Katherine L. Harry, Joel Miscall, Nicholas A. Rorrer, Garret M. Miyake

{"title":"Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols","authors":"Xin Liu, Zhitao Hu, Emma M. Rettner, Katherine L. Harry, Joel Miscall, Nicholas A. Rorrer, Garret M. Miyake","doi":"10.1038/s41557-025-01753-8","DOIUrl":"10.1038/s41557-025-01753-8","url":null,"abstract":"Petroleum-derived polyolefins exhibit diverse properties and are the most important and largest volume class of plastics. However, polyolefins are difficult to efficiently recycle or break down and are now a persistent global contaminant. Broadly replacing polyolefins with bio-derived and degradable polyethylene-like materials is an important yet challenging endeavour towards sustainable plastics. Here we report a solution for circular bio-based polyethylene-like materials synthesized by acceptorless dehydrogenative polymerization from linear and branched diols and their catalytic closed-loop recycling. The polymerization and depolymerization processes utilize earth-abundant manganese complexes as catalysts. These materials exhibit a wide range of mechanical properties, encompassing thermoplastics to plastomers to elastomers. The branched diols, produced through a thiol–ene click reaction, can be polymerized to plastics with significantly enhanced tensile properties, toughness and adhesive properties. These materials could be depolymerized back to monomers through hydrogenation and were separatable with a monomer recovery of up to 99%, unaffected by the presence of dyes and additives. Overall, this system establishes a route to more sustainable plastics. Bio-based polyethylene-like materials with tunable thermal and mechanical properties have been synthesized from plant-derived diols using an acceptorless dehydrogenative polymerization strategy. Now it has been shown that this atom-economical and mass-economical approach employing non-precious metal catalysts enables closed-loop recycling and advances sustainable solutions for the circular plastic economy.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 4","pages":"500-506"},"PeriodicalIF":19.2,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462134","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

Site-specific activation of the proton pump inhibitor rabeprazole by tetrathiolate zinc centres 四硫酸锌中心对质子泵抑制剂雷贝拉唑的位点特异性激活

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-20 DOI: 10.1038/s41557-025-01745-8

Teresa Marker, Raphael R. Steimbach, Cecilia Perez-Borrajero, Marcin Luzarowski, Eric Hartmann, Sibylle Schleich, Daniel Pastor-Flores, Elisa Espinet, Andreas Trumpp, Aurelio A. Teleman, Frauke Gräter, Bernd Simon, Aubry K. Miller, Tobias P. Dick

{"title":"Site-specific activation of the proton pump inhibitor rabeprazole by tetrathiolate zinc centres","authors":"Teresa Marker, Raphael R. Steimbach, Cecilia Perez-Borrajero, Marcin Luzarowski, Eric Hartmann, Sibylle Schleich, Daniel Pastor-Flores, Elisa Espinet, Andreas Trumpp, Aurelio A. Teleman, Frauke Gräter, Bernd Simon, Aubry K. Miller, Tobias P. Dick","doi":"10.1038/s41557-025-01745-8","DOIUrl":"10.1038/s41557-025-01745-8","url":null,"abstract":"Proton pump inhibitors have become top-selling drugs worldwide. Serendipitously discovered as prodrugs that are activated by protonation in acidic environments, proton pump inhibitors inhibit stomach acid secretion by covalently modifying the gastric proton pump. Despite their widespread use, alternative activation mechanisms and potential target proteins in non-acidic environments remain poorly understood. Employing a chemoproteomic approach, we found that the proton pump inhibitor rabeprazole selectively forms covalent conjugates with zinc-binding proteins. Focusing on DENR, a protein with a C4 zinc cluster (that is, zinc coordinated by four cysteines), we show that rabeprazole is activated by the zinc ion and subsequently conjugated to zinc-coordinating cysteines. Our results suggest that drug binding, activation and conjugation take place rapidly within the zinc coordination sphere. Finally, we provide evidence that other proton pump inhibitors can be activated in the same way. We conclude that zinc acts as a Lewis acid, obviating the need for low pH, to promote the activation and conjugation of proton pump inhibitors in non-acidic environments. Proton pump inhibitors (PPIs) are prodrugs that are activated by protonation in the highly acidic environment of the stomach lining. Now, coordination of PPIs to protein-bound zinc ions is revealed as another pathway to PPI activation. Acting as a Lewis acid, the zinc ion facilitates conjugation of the drug to zinc-coordinating cysteine residues.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 4","pages":"507-517"},"PeriodicalIF":19.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-025-01745-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452177","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}

引用次数: 0