Nature synthesis最新文献_第5页

Synthesis of oligomers with control of the monomer sequence and chirality 控制单体序列和手性的低聚物的合成

IF 2

Nature synthesis Pub Date : 2025-06-16 DOI: 10.1038/s44160-025-00806-7

引用次数: 0

Isolated carbon(I) species featuring a carbone cation radical 具有碳正离子自由基的分离碳(I)种

IF 2

Nature synthesis Pub Date : 2025-06-13 DOI: 10.1038/s44160-025-00824-5

Yi-Chen Chan, He-Xin Xiao, Lei Qin, Jiun-Shian Shen, Chen-Rui Yang, Glenn P. A. Yap, Wei-Min Ching, Wen-Ching Chen, Yun-Wei Chiang, Gernot Frenking, Lili Zhao, Tiow-Gan Ong

{"title":"Isolated carbon(I) species featuring a carbone cation radical","authors":"Yi-Chen Chan, He-Xin Xiao, Lei Qin, Jiun-Shian Shen, Chen-Rui Yang, Glenn P. A. Yap, Wei-Min Ching, Wen-Ching Chen, Yun-Wei Chiang, Gernot Frenking, Lili Zhao, Tiow-Gan Ong","doi":"10.1038/s44160-025-00824-5","DOIUrl":"10.1038/s44160-025-00824-5","url":null,"abstract":"Carbynes, characterized by their radical and carbene attributes, possess three non-bonding electrons and have garnered substantial scientific interest. The high reactivity and complex hybridization of valence orbitals in carbynes have impeded the isolation of free carbon(I) species. Carbodicarbenes are divalent carbon(0) species with two electron lone pairs, which are in principle capable of losing an electron to generate a radical cation carbon(I) species containing three non-bonded electrons, similar to the frontier orbital of a carbyne without a vacant orbital. Here we describe the isolation of a crystalline cation radical carbon(I), [1-CDC]•+, prepared by a single-electron transfer between a carbodicarbene and a nitroaromatic compound to generate a stable radical ionic pair. Electron paramagnetic resonance and X-ray crystallography with quantum chemical analysis show that the unpaired electron of [1-CDC]•+ resides in the p(π) atomic orbital of the secondary carbon with some delocalization to the N-heterocyclic carbene ligands. Exploring the reactivity of this carbon(I) radical cation revealed its capacity to mediate a variety of C–O and C–C cross-coupling reactions with electron-deficient aryl halides. These findings not only expand the understanding of carbon(I) radical chemistry but also potentially open new avenues for radical methodologies in organic synthesis and catalysis. The isolation of a crystalline radical cation carbon(I) species, generated via single-electron transfer between a carbodicarbene and a nitroaromatic compound, is reported. The resulting radical ion pair can mediate various C–O and C–C cross-coupling reactions with electron-deficient arenes bearing a leaving group.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1278-1287"},"PeriodicalIF":20.0,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Combining oxygen reduction with glycerol oxidation in a galvanic device 在电装置中将氧还原与甘油氧化相结合

IF 2

Nature synthesis Pub Date : 2025-06-11 DOI: 10.1038/s44160-025-00831-6

Hui Luo, Jesús Barrio

引用次数: 0

Chemoenzymatic platform with coordinated cofactor self-circulation for lignin valorization 具有协同辅因子自循环的木质素增值化学酶平台

IF 2

Nature synthesis Pub Date : 2025-06-10 DOI: 10.1038/s44160-025-00819-2

Liangxu Liu, Xiaotong Wang, Yeyun Wu, Hengrun Li, Jiawei Wang, Chaofeng Li, Haotian Zheng, Jun Ni

{"title":"Chemoenzymatic platform with coordinated cofactor self-circulation for lignin valorization","authors":"Liangxu Liu, Xiaotong Wang, Yeyun Wu, Hengrun Li, Jiawei Wang, Chaofeng Li, Haotian Zheng, Jun Ni","doi":"10.1038/s44160-025-00819-2","DOIUrl":"10.1038/s44160-025-00819-2","url":null,"abstract":"Lignin valorization is vital for achieving economically viable and sustainable lignocellulosic biorefineries. However, the value-added utilization of lignin constituents is hampered by the requirement of expensive cofactors and low conversions. Here, by integrating coenzyme regeneration and cell-free expression, we report an in vitro multienzyme-coordinated expression with cofactor self-circulation (iMECS) strategy to achieve efficient lignin-to-molecule conversion. The iMECS system established a catalytic bridge with high atom economy for converting lignin waste into valuable aromatic compounds. Curcumin, vanillin and raspberry ketone were efficiently synthesized in a coenzyme-free manner, with a conversion of over 90%. We also demonstrated the flexibility of the iMECS platform, through which a wide array of phenylpropanoids could be easily obtained by enzyme swapping and pathway extension. By integrating chemical depolymerization with the iMECS system, lignin-rich agricultural waste was directly converted into valuable chemicals, and the overall catalytic efficiency was enhanced by up to 48-fold compared with the reported titres. This efficient, general platform can facilitate the utilization of lignocellulosic biomass, thereby promoting zero-waste biorefineries for a more sustainable future. Lignin valorization is hampered by the requirement for expensive cofactors and low conversions. Now a chemoenzymatic platform with coordinated cofactor self-circulation for realizing efficient lignin-to-molecule conversion is reported, facilitating the advancement of sustainable biorefineries.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1151-1160"},"PeriodicalIF":20.0,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stereospecific synthesis of spiro-bridged conjugated carbocycles 螺旋桥接共轭碳环的立体定向合成

IF 2

Nature synthesis Pub Date : 2025-06-06 DOI: 10.1038/s44160-025-00818-3

引用次数: 0

A dendritic structure for organic solar cells 有机太阳能电池的树突结构

IF 2

Nature synthesis Pub Date : 2025-06-05 DOI: 10.1038/s44160-025-00829-0

Joel Cejas-Sánchez

引用次数: 0

Magnonic V(tetracyanoethylene)2 thin films 磁振子V（四氰乙烯）2薄膜

IF 2

Nature synthesis Pub Date : 2025-06-04 DOI: 10.1038/s44160-025-00830-7

Alexandra R. Groves

引用次数: 0

Thianthrenium-enabled modular synthesis of bicyclo[1.1.1]pentanes 双[1.1.1]戊烷的硫鎓化模块化合成

IF 2

Nature synthesis Pub Date : 2025-06-04 DOI: 10.1038/s44160-025-00821-8

Zibo Bai, Zikuan Wang, Thomas Hin-Fung Wong, Tobias Ritter

{"title":"Thianthrenium-enabled modular synthesis of bicyclo[1.1.1]pentanes","authors":"Zibo Bai, Zikuan Wang, Thomas Hin-Fung Wong, Tobias Ritter","doi":"10.1038/s44160-025-00821-8","DOIUrl":"10.1038/s44160-025-00821-8","url":null,"abstract":"The incorporation of three-dimensional small-ring scaffolds into bioactive molecules can enhance metabolic stability and solubility. Over the last decade, 1,3-disubstituted bicyclo[1.1.1]pentanes (BCPs) have emerged as valuable bioisosteres for para-substituted benzene rings in drug discovery. However, BCP synthesis typically requires de novo synthesis from volatile [1.1.1]propellane, whereas more stable BCP reagents, such as alkyl BCP iodides, allow modification at only one end, limiting their application to end groups. Here we describe a stable, bifunctional iodobicyclo[1.1.1]pentylmethyl thianthrenium (IBM-TT+) reagent for modular BCP bioisostere production. The cationic thianthrenium group at the neopentyl site of IBM-TT+ facilitates chemoselective substitutions through electrostatic interactions, overcoming the high energy barriers of bimolecular nucleophilic substitution (SN2) at neopentyl sites. The retained BCP iodide functionality serves as a second versatile handle for metal–halogen exchange, photoredox chemistry or transition-metal catalysis. The dual reactivity of IBM-TT+ allows synthesis of a multitude of BCP bioisosteres for benzyl amines, ethers, esters, thioethers and diarylmethanes. The lack of stable and versatile bicyclo[1.1.1]pentyl reagents hinders their broader adoption as aryl bioisosteres in drug discovery. Now, a stable, bifunctional iodobicyclo[1.1.1]pentylmethyl thianthrenium (IBM-TT+) reagent is developed for modular bicyclo[1.1.1]pentane bioisostere production.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1161-1169"},"PeriodicalIF":20.0,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00821-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stacks of carpyridine and water 成堆的吡啶和水

IF 2

Nature synthesis Pub Date : 2025-06-04 DOI: 10.1038/s44160-025-00828-1

Peter W. Seavill

引用次数: 0

Synthesis of chiral sequence-defined oligomers via sulfur–fluoride and sulfur–phenolate exchange reactions 通过氟化硫和硫酚交换反应合成手性顺序确定的低聚物

IF 2

Nature synthesis Pub Date : 2025-06-02 DOI: 10.1038/s44160-025-00805-8

Yu Han, Sidharam P. Pujari, Muthusamy Subramaniam, Bo Chen, Fedor M. Miloserdov, Han Zuilhof

{"title":"Synthesis of chiral sequence-defined oligomers via sulfur–fluoride and sulfur–phenolate exchange reactions","authors":"Yu Han, Sidharam P. Pujari, Muthusamy Subramaniam, Bo Chen, Fedor M. Miloserdov, Han Zuilhof","doi":"10.1038/s44160-025-00805-8","DOIUrl":"10.1038/s44160-025-00805-8","url":null,"abstract":"Sequence-defined oligomers have been synthesized with increasing complexity, but the participation of chiral centres in the oligomerization process remains challenging. Here we report the synthesis of sequence-defined oligosulfonimidates (up to thirteen-mers) obtained via a series of sulfur–fluoride exchange and sulfur–phenolate exchange reactions. Next, we demonstrate that the use of chiral sulfonimidoyl fluorides allows the construction of chiral oligomers, in which the chirality of each linking S-centred site can be tuned independently of the rest of the molecule, thereby opening a way to a potentially vast increase in the information density of such oligomers. Finally, by activating a dormant fluorous tag used for the separation of oligomers, a tail-to-head-type sulfur–phenolate exchange polymerization strategy was developed using these oligomers, resulting in sequence-controlled polymers. The high variability of sulfonimidates and the chiral control provided to macromolecules through this technique results in another step towards full control over nature-mimicking polymers. Precise control over both sequence and chirality remains a challenge in polymer chemistry. Here sulfur–fluoride exchange and sulfur–phenolate exchange reactions are used to create chiral oligosulfonimidates with tunable sulfur-centred chirality. This strategy enables precise three-dimensional structural control over oligomers and polymers, marking a step towards fully nature-mimicking macromolecules.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1106-1117"},"PeriodicalIF":20.0,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00805-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123689","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0