Nature chemistry最新文献_第2页

Photomediated aliphatic C–H functionalization

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

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

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Light-activated hypervalent iodine agents enable diverse aliphatic C–H functionalization

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

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 21.8 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":"https://doi.org/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.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"50 1","pages":""},"PeriodicalIF":21.8,"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

IF 21.8 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":"https://doi.org/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.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"31 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Rotaxanes with amphoteric σ-hole donors for cation or anion recognition

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-20 DOI: 10.1038/s41557-025-01743-w

引用次数: 0

Moiré two-dimensional covalent organic framework superlattices

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-02-20 DOI: 10.1038/s41557-025-01748-5

Gaolei Zhan, Brecht Koek, Yijia Yuan, Yikuan Liu, Vipin Mishra, Veniero Lenzi, Karol Strutyński, Chunxiao Li, Rongrong Zhang, Xin Zhou, Hwa Seob Choi, Zhen-Feng Cai, Joaquín Almarza, Kunal S. Mali, Aurelio Mateo-Alonso, Manuel Melle Franco, Yihan Zhu, Steven De Feyter, Kian Ping Loh

{"title":"Moiré two-dimensional covalent organic framework superlattices","authors":"Gaolei Zhan, Brecht Koek, Yijia Yuan, Yikuan Liu, Vipin Mishra, Veniero Lenzi, Karol Strutyński, Chunxiao Li, Rongrong Zhang, Xin Zhou, Hwa Seob Choi, Zhen-Feng Cai, Joaquín Almarza, Kunal S. Mali, Aurelio Mateo-Alonso, Manuel Melle Franco, Yihan Zhu, Steven De Feyter, Kian Ping Loh","doi":"10.1038/s41557-025-01748-5","DOIUrl":"https://doi.org/10.1038/s41557-025-01748-5","url":null,"abstract":"The on-surface synthesis of two-dimensional (2D) polymers from monomers represents a useful strategy for designing lattice, orbital and spin symmetries. Like other 2D materials, the ordered stacking of 2D polymers into bilayers may allow developing unique optoelectronic, charge transport and magnetic properties not found in the individual layers. However, controlling layer stacking of 2D polymers remains challenging. Here we describe a method for synthesizing 2D polymer bilayers or bilayer 2D covalent organic frameworks at the liquid–substrate interface through the direct condensation of monomers. More importantly, we also show how factors such as monomer structure and solvent mixture influence the bilayer stacking modes and how, under certain conditions, large-area moiré superlattices emerge from the twisted bilayer stacking. This finding offers new opportunities for the design of bilayer stacked framework materials with tunable electronic and structural properties.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"29 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452167","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

Catalytic difluorocarbene insertion enables access to fluorinated oxetane isosteres

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-02-20 DOI: 10.1038/s41557-024-01730-7

Tong-De Tan, Fang Zhou, Kevin P. Quirion, Yu-Qi Wang, Daniel Zhi Wei Ng, Xiaohua Luo, Eric Chun Yong Chan, Peng Liu, Ming Joo Koh

{"title":"Catalytic difluorocarbene insertion enables access to fluorinated oxetane isosteres","authors":"Tong-De Tan, Fang Zhou, Kevin P. Quirion, Yu-Qi Wang, Daniel Zhi Wei Ng, Xiaohua Luo, Eric Chun Yong Chan, Peng Liu, Ming Joo Koh","doi":"10.1038/s41557-024-01730-7","DOIUrl":"https://doi.org/10.1038/s41557-024-01730-7","url":null,"abstract":"Skeletal editing of heterocyclic building blocks offers an appealing way to expand the accessible chemical space by diversifying molecular scaffolds for drug discovery. Despite the recent boom in this area, catalytic strategies that directly introduce fluorine into the backbone of small-ring heterocycles remain rare owing to the challenges of strain-induced ring cleavage and defluorination. Here we describe a copper-catalysed approach for skeletal expansion of oxygen heterocycles by reaction with a difluorocarbene species generated in situ to induce carbon atom insertion. The α,α-difluoro-oxetane products are potential surrogates of oxetane, β-lactone and carbonyl pharmacophores on the basis of their computed molecular properties and electrostatic potential maps. The utility of this approach is highlighted by synthesis of various drug-like molecules and fluorinated isosteres of biologically active compounds. Experimental and computational investigations provide insight into the mechanism and the unique role of the copper catalyst in promoting both ring-opening and cyclization steps of the reaction.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"19 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452166","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

Amphoteric chalcogen-bonding and halogen-bonding rotaxanes for anion or cation recognition

IF 19.2 1区化学

Nature chemistry Pub Date : 2025-02-20 DOI: 10.1038/s41557-025-01742-x

Yuen Cheong Tse, Andrew Docker, Igor Marques, Vítor Félix, Paul D. Beer

{"title":"Amphoteric chalcogen-bonding and halogen-bonding rotaxanes for anion or cation recognition","authors":"Yuen Cheong Tse, Andrew Docker, Igor Marques, Vítor Félix, Paul D. Beer","doi":"10.1038/s41557-025-01742-x","DOIUrl":"10.1038/s41557-025-01742-x","url":null,"abstract":"The ever-increasing demand in the development of host molecules for the recognition of charged species is stimulated by their fundamental roles in numerous biological and environmental processes. Here, capitalizing on the inherent amphoteric nature of anisotropically polarized tellurium or iodine atoms, we demonstrate a proof of concept in charged guest recognition, where the same neutral host structure binds both cations or anions solely through its chalcogen or halogen donor atoms. Through extensive 1H nuclear magnetic resonance titration experiments and computational density functional theory studies, a library of chalcogen-bonding (ChB) and halogen-bonding (XB) mechanically interlocked [2]rotaxane molecules, including seminal examples of all-ChB and mixed ChB/XB [2]rotaxanes, are shown to function as either Lewis-acidic or Lewis-basic multidentate hosts for selective halide anion and metal cation binding. Notably, the exploitation of the inherent amphoteric character of an atom for the strategic purpose of either cation or anion recognition constitutes the inception of a previously unexplored area of supramolecular host–guest chemistry. The importance of charged species in numerous biological and environmental processes has stimulated the development of host molecules for their selective recognition. Now anisotropically polarized halogen- and chalcogen-bonding [2]rotaxanes are demonstrated to exhibit dual Lewis-acidic and Lewis-basic amphoteric properties for anion or cation recognition via the same donor atoms.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 3","pages":"373-381"},"PeriodicalIF":19.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-025-01742-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452168","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