Pub Date : 2026-01-05DOI: 10.1038/s44160-025-00966-6
Karl Adrian Gandionco, Zhiyuan Zhang, Jongwoo Lim
The strategic placement of sulfur within a nickel porphyrin complex coupled with copper facilitates efficient electrochemical CO2 reduction to ethylene and ethanol.
硫在镍卟啉络合物与铜偶联的战略位置有利于有效的电化学CO2还原为乙烯和乙醇。
{"title":"Sulfur enhances electrochemical CO2 reduction over porphyrin catalysts","authors":"Karl Adrian Gandionco, Zhiyuan Zhang, Jongwoo Lim","doi":"10.1038/s44160-025-00966-6","DOIUrl":"10.1038/s44160-025-00966-6","url":null,"abstract":"The strategic placement of sulfur within a nickel porphyrin complex coupled with copper facilitates efficient electrochemical CO2 reduction to ethylene and ethanol.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"156-157"},"PeriodicalIF":20.0,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903319","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}
Pub Date : 2026-01-02DOI: 10.1038/s44160-025-00961-x
Jing Li, Kedang Chen, Nathan E. Soland, Jindou Yang, Yuanzuo Gao, Seonjeong Cheon, Yuming Su, Peidong Yang, Hailiang Wang
Sustainable synthesis of C5+ carbohydrates from CO2 remains challenging due to the complexity of controlled CO2 reduction and carbon–carbon coupling. Biochemical approaches can convert primary CO2 reduction products into C5+ carbohydrates, but are often constrained by lengthy reaction periods, low production rates and system complexity. Here we present a two-step electrochemical reduction–formose reaction method that uses hydroxymethanesulfonate (HMS) as a more stable surrogate for formaldehyde to facilitate the direct synthesis of C5+ carbohydrates from electrochemically fixed CO2. Using cobalt tetraaminophthalocyanine molecules supported on multiwalled carbon nanotubes as an electrocatalyst, we achieve an HMS Faradaic efficiency of ~12% at a total current density of 150 mA cm−2. Employing direct CO reduction increases the Faradaic efficiency to ~25% with over 63% carbon efficiency. The produced HMS enables an efficient formose reaction under mild conditions reaching a yield of 20.4% for C5+ carbohydrates. The CO2-derived HMS also demonstrates its versatility as a formaldehyde surrogate in other reactions for synthesizing various valuable chemical products, promising a new approach for feeding advanced chemical synthesis with electrochemically fixed CO2 via the intercepted formaldehyde intermediate.
由于可控CO2还原和碳-碳耦合的复杂性，从CO2中可持续合成C5+碳水化合物仍然具有挑战性。生物化学方法可以将初级CO2还原产物转化为C5+碳水化合物，但往往受到反应周期长、生产率低和系统复杂性的限制。本文提出了一种两步电化学还原-福尔摩斯反应方法，该方法使用羟基甲烷磺酸盐（HMS）作为更稳定的甲醛替代物，促进了由电化学固定CO2直接合成C5+碳水化合物。利用负载在多壁碳纳米管上的四氨基酞菁钴分子作为电催化剂，在总电流密度为150 mA cm−2时，我们实现了约12%的HMS法拉第效率。采用直接CO还原法可使法拉第效率提高到25%，碳效率超过63%。所制备的HMS能在温和条件下对C5+碳水化合物进行高效的福尔斯反应，产率达20.4%。二氧化碳衍生的HMS还证明了其作为甲醛替代品的多功能性，可以在其他反应中合成各种有价值的化学产品，这为通过截获的甲醛中间体进行电化学固定CO2的高级化学合成提供了新的途径。
{"title":"Artificial synthesis of carbohydrates from electrochemically fixed carbon dioxide","authors":"Jing Li, Kedang Chen, Nathan E. Soland, Jindou Yang, Yuanzuo Gao, Seonjeong Cheon, Yuming Su, Peidong Yang, Hailiang Wang","doi":"10.1038/s44160-025-00961-x","DOIUrl":"https://doi.org/10.1038/s44160-025-00961-x","url":null,"abstract":"Sustainable synthesis of C5+ carbohydrates from CO2 remains challenging due to the complexity of controlled CO2 reduction and carbon–carbon coupling. Biochemical approaches can convert primary CO2 reduction products into C5+ carbohydrates, but are often constrained by lengthy reaction periods, low production rates and system complexity. Here we present a two-step electrochemical reduction–formose reaction method that uses hydroxymethanesulfonate (HMS) as a more stable surrogate for formaldehyde to facilitate the direct synthesis of C5+ carbohydrates from electrochemically fixed CO2. Using cobalt tetraaminophthalocyanine molecules supported on multiwalled carbon nanotubes as an electrocatalyst, we achieve an HMS Faradaic efficiency of ~12% at a total current density of 150 mA cm−2. Employing direct CO reduction increases the Faradaic efficiency to ~25% with over 63% carbon efficiency. The produced HMS enables an efficient formose reaction under mild conditions reaching a yield of 20.4% for C5+ carbohydrates. The CO2-derived HMS also demonstrates its versatility as a formaldehyde surrogate in other reactions for synthesizing various valuable chemical products, promising a new approach for feeding advanced chemical synthesis with electrochemically fixed CO2 via the intercepted formaldehyde intermediate.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"14 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895507","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}
Polyethylene-like materials consist of long-chain oligoethylene blocks and chemically cleavable linkages, providing a promising alternative to chemically inert polyethylene while retaining comparable properties. Larger and uniform chain lengths of oligoethylene blocks are preferred to retain polyethylene crystallinity; however, the efficient synthesis of uniform ultralong oligoethylenes with guaranteed purity remains challenging. Here we report the precision synthesis of uniform oligoethylenes of up to 576 carbon atoms based on the Julia–Kocienski reaction. Using these as building blocks, a series of high-density polyethylene-like materials with regularly distributed ester linkages were developed. The oligoethylene with 126 carbon atoms readily affords remarkable thermal (Tm ≈ 130 °C) and mechanical properties. Due to the uniformity of oligoethylene blocks, closed-loop chemical recyclability of high-density polyethylene-like materials is possible for at least five cycles, excluding compositional heterogeneity and batch-to-batch fluctuation. Our strategy for constructing uniform oligoethylenes with exceptionally high chain lengths is interesting for new-generation recyclable materials.
{"title":"Synthesis of discrete oligoethylenes towards chemically recyclable polyolefins","authors":"Rui Tan, Yanru An, Yuxin Liu, Xiaojie Yang, Qinmeng Zhong, Xinyue Yan, Yuxiao Hu, Minglong Chen, Jie Cen, Xiaoman Huang, Gefei Wang, Jinming Hu, Shiyong Liu, Zhengbiao Zhang","doi":"10.1038/s44160-025-00955-9","DOIUrl":"https://doi.org/10.1038/s44160-025-00955-9","url":null,"abstract":"Polyethylene-like materials consist of long-chain oligoethylene blocks and chemically cleavable linkages, providing a promising alternative to chemically inert polyethylene while retaining comparable properties. Larger and uniform chain lengths of oligoethylene blocks are preferred to retain polyethylene crystallinity; however, the efficient synthesis of uniform ultralong oligoethylenes with guaranteed purity remains challenging. Here we report the precision synthesis of uniform oligoethylenes of up to 576 carbon atoms based on the Julia–Kocienski reaction. Using these as building blocks, a series of high-density polyethylene-like materials with regularly distributed ester linkages were developed. The oligoethylene with 126 carbon atoms readily affords remarkable thermal (Tm ≈ 130 °C) and mechanical properties. Due to the uniformity of oligoethylene blocks, closed-loop chemical recyclability of high-density polyethylene-like materials is possible for at least five cycles, excluding compositional heterogeneity and batch-to-batch fluctuation. Our strategy for constructing uniform oligoethylenes with exceptionally high chain lengths is interesting for new-generation recyclable materials.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"22 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895508","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}
Pub Date : 2026-01-02DOI: 10.1038/s44160-025-00960-y
Shun Kashiwaya, Yuchen Shi, Jun Lu, Davide G. Sangiovanni, Grzegorz Greczynski, Martin Magnuson, Mike Andersson, Johanna Rosen, Lars Hultman
{"title":"Reply to: Synthesis of goldene comprising single-atom layer gold","authors":"Shun Kashiwaya, Yuchen Shi, Jun Lu, Davide G. Sangiovanni, Grzegorz Greczynski, Martin Magnuson, Mike Andersson, Johanna Rosen, Lars Hultman","doi":"10.1038/s44160-025-00960-y","DOIUrl":"https://doi.org/10.1038/s44160-025-00960-y","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895506","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}
{"title":"Divergent synthesis of N heterocycles from carbocycles enabled by electrochemical nitrogen atom insertion","authors":"Guo-Quan Sun, Xiyan Wang, Rui Hu, Weidong Rao, Yu Zhao, Ming Joo Koh","doi":"10.1038/s44160-025-00945-x","DOIUrl":"https://doi.org/10.1038/s44160-025-00945-x","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771364","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}
Pub Date : 2025-12-16DOI: 10.1038/s44160-025-00925-1
Yilin Cao, Warabhorn Rodphon, Turki M. Alturaifi, Al Vicente Riano D. Lisboa, Zhouyang Ren, Job J. C. Struijs, Hui-Qi Ni, Taras Savchuk, Richard P. Loach, Shouliang Yang, Indrawan J. McAlpine, Donna G. Blackmond, Pavel K. Mykhailiuk, Peng Liu, K. Barry Sharpless, Keary M. Engle
Here we present the ambiphilic reactivity of alkyl sulfonyl fluorides in the stereoselective synthesis of diverse cyclopropanes from olefins, under palladium(II) catalysis. The sulfonyl fluoride functionality serves as both an acidifying group and an internal oxidant within the ambiphile, enabling successive carbopalladation and oxidative addition steps in the catalytic cycle, respectively. The transformation grants access to cis-substituted cyclopropanes and exhibits broad compatibility with various alkyl sulfonyl fluorides, including those bearing –CN, –CO2R, isoxazolyl, pyrazolyl and aryl groups. With internal alkene substrates, 1,2,3-trisubstituted cyclopropanes that are otherwise challenging to synthesize are formed in good-to-moderate yields and predictable diastereoselectivity. Detailed mechanistic insights from reaction progress kinetic analysis and density functional theory calculations reveal that the SN2-type C–SO2F oxidative addition is the turnover-limiting and diastereoselectivity-determining step. The ambiphilic reactivity of alkyl sulfonyl fluorides in stereoselective cyclopropanation under Pd(II) catalysis is reported. The method provides convenient access to cis-disubstituted cyclopropanes that are otherwise challenging to access. A representative carboxylic acid cyclopropane building block is scaled up to 100 mmol, demonstrating the practicality of this transformation.
{"title":"Alkyl sulfonyl fluorides as ambiphiles in the stereoselective palladium(II)-catalysed cyclopropanation of unactivated alkenes","authors":"Yilin Cao, Warabhorn Rodphon, Turki M. Alturaifi, Al Vicente Riano D. Lisboa, Zhouyang Ren, Job J. C. Struijs, Hui-Qi Ni, Taras Savchuk, Richard P. Loach, Shouliang Yang, Indrawan J. McAlpine, Donna G. Blackmond, Pavel K. Mykhailiuk, Peng Liu, K. Barry Sharpless, Keary M. Engle","doi":"10.1038/s44160-025-00925-1","DOIUrl":"10.1038/s44160-025-00925-1","url":null,"abstract":"Here we present the ambiphilic reactivity of alkyl sulfonyl fluorides in the stereoselective synthesis of diverse cyclopropanes from olefins, under palladium(II) catalysis. The sulfonyl fluoride functionality serves as both an acidifying group and an internal oxidant within the ambiphile, enabling successive carbopalladation and oxidative addition steps in the catalytic cycle, respectively. The transformation grants access to cis-substituted cyclopropanes and exhibits broad compatibility with various alkyl sulfonyl fluorides, including those bearing –CN, –CO2R, isoxazolyl, pyrazolyl and aryl groups. With internal alkene substrates, 1,2,3-trisubstituted cyclopropanes that are otherwise challenging to synthesize are formed in good-to-moderate yields and predictable diastereoselectivity. Detailed mechanistic insights from reaction progress kinetic analysis and density functional theory calculations reveal that the SN2-type C–SO2F oxidative addition is the turnover-limiting and diastereoselectivity-determining step. The ambiphilic reactivity of alkyl sulfonyl fluorides in stereoselective cyclopropanation under Pd(II) catalysis is reported. The method provides convenient access to cis-disubstituted cyclopropanes that are otherwise challenging to access. A representative carboxylic acid cyclopropane building block is scaled up to 100 mmol, demonstrating the practicality of this transformation.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"281-289"},"PeriodicalIF":20.0,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00925-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771135","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}
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