Nature synthesis最新文献_第8页

A selenium-mediated layer-by-layer synthetic strategy for multilayered multicomponent nanocrystals 硒介导的多层多组分纳米晶体逐层合成策略

Nature synthesis Pub Date : 2024-07-03 DOI: 10.1038/s44160-024-00598-2

Chun Hu, Yangyang Zhang, Renjie Ren, Jijian Xu, Lijia Liu, Qingyu Kong, Zhiwei Hu, Shijian Zheng, Lin Zhuang, Jian Huang, Yuanzhi Tan, Xiaoqing Huang

{"title":"A selenium-mediated layer-by-layer synthetic strategy for multilayered multicomponent nanocrystals","authors":"Chun Hu, Yangyang Zhang, Renjie Ren, Jijian Xu, Lijia Liu, Qingyu Kong, Zhiwei Hu, Shijian Zheng, Lin Zhuang, Jian Huang, Yuanzhi Tan, Xiaoqing Huang","doi":"10.1038/s44160-024-00598-2","DOIUrl":"10.1038/s44160-024-00598-2","url":null,"abstract":"Ordered heterostructured nanocrystals with large compositional and morphological diversity are important for many applications. However, design of multicomponent nanostructures at the atomic level is difficult due to the elusive nucleation and growth processes in a solution-phase environment. Here we report a modular synthetic protocol that produces ordered multilayered nanostructures with small particle size by layer-by-layer growth. We introduce a selenium capping agent to hinder self-assembly, aggregation and phase segregation of nanostructures, while also sequencing the priority of metal atoms that migrate in the substrate lattice according to different metal–selenium bonding strengths, leading to a layer-by-layer growth for ordered nanostructures. The multilayered multicomponent nanocrystals are demonstrated in an alkaline polymer electrolyte fuel cell by using PtRuZn-SKE (SKE, selenium-mediated Kirkendall effect) as the anodic hydrogen oxidation reaction catalyst, which can deliver a high peak power density of 1.52 W cm−2 in H2–O2 and 1.12 W cm−2 in H2–air (CO2-free) while operating at 600 mA cm−2 for 100 h. This generalizable strategy provides a predictable synthetic pathway to complex nanocrystals. A modular synthetic procedure is reported in which a selenium capping agent hinders phase segregation and aggregation while sequencing the priority of metals that migrate into the substrate lattice, leading to a layer-by-layer growth of ordered nanostructures.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1299-1309"},"PeriodicalIF":0.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510596","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

Oxidative coupling for urea synthesis 用于尿素合成的氧化偶联

Nature synthesis Pub Date : 2024-07-03 DOI: 10.1038/s44160-024-00611-8

Peter W. Seavill

引用次数: 0

Interdiffusion-enhanced cation exchange for HgSe and HgCdSe nanocrystals with infrared bandgaps 具有红外带隙的 HgSe 和 HgCdSe 纳米晶体的互扩散增强型阳离子交换

Nature synthesis Pub Date : 2024-07-03 DOI: 10.1038/s44160-024-00597-3

Wonseok Lee, Andrew M. Smith

{"title":"Interdiffusion-enhanced cation exchange for HgSe and HgCdSe nanocrystals with infrared bandgaps","authors":"Wonseok Lee, Andrew M. Smith","doi":"10.1038/s44160-024-00597-3","DOIUrl":"10.1038/s44160-024-00597-3","url":null,"abstract":"Colloidal semiconductor nanocrystals based on CdSe have been precisely optimized for photonic applications in the visible spectrum, with modern products exhibiting structural uniformity, near 100% quantum yield and linewidths narrower than 100 meV. Here we report homogeneous nanocrystals with tunable bandgaps in the infrared spectrum based on HgSe and HgxCd1−xSe alloys deriving from CdSe precursors. We find that Ag+ catalyses cation interdiffusion to reduce the CdSe–HgSe alloying temperature from 250 °C to 80 °C. Together with ligands that modulate surface cation exchange rates, interdiffusion-enhanced Hg2+ exchange of diverse CdSe nanocrystals proceeds homogeneously and completely. The products retain the size, shape and uniformity of the parent nanocrystals but exhibit enhanced absorption. After passivation with heteroepitaxial CdZnS shells, photoluminescence wavelengths are tunable in the shortwave infrared by composition without changing size, with 80–91% quantum yield and linewidths near 100 meV. These materials may find applications in infrared photonic devices and infrared bioimaging. CdSe nanocrystals are used as synthetic templates for HgSe and alloyed HgxCd1−xSe nanocrystals with tunable, diverse structures. Cd2+-to-Hg2+ exchange occurs homogeneously and completely through interdiffusion enhancement with Ag+ catalysts and with surface cation exchange modulated by alkylthiol ligands.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1243-1254"},"PeriodicalIF":0.0,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530219","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

Chemoenzymatic synthesis of macrocycles via dynamic kinetic resolution of secondary alcohols 通过仲醇的动态动力学解析化学合成大环

Nature synthesis Pub Date : 2024-07-02 DOI: 10.1038/s44160-024-00591-9

Javier Guerrero-Morales, Marie Scaglia, Edouard Fauran, Guillaume Lepage, Shawn K. Collins

{"title":"Chemoenzymatic synthesis of macrocycles via dynamic kinetic resolution of secondary alcohols","authors":"Javier Guerrero-Morales, Marie Scaglia, Edouard Fauran, Guillaume Lepage, Shawn K. Collins","doi":"10.1038/s44160-024-00591-9","DOIUrl":"10.1038/s44160-024-00591-9","url":null,"abstract":"Macrolactones are privileged motifs in materials science, aromachemicals and pharmaceuticals. The pivotal ester linkage is often formed from chiral secondary alcohols, with macrolactonization using stoichiometric reagents to ensure retention or inversion of stereochemistry without compromising enantiopurity. An ideal strategy for macrolactonization is via dynamic kinetic resolution (DKR), which involves the simultaneous formation of the ester bond and introduction of a chiral centre with high stereocontrol. Surprisingly, a DKR method within the context of macrocyclization is yet to be reported. Here, using a chemoenzymatic approach, the macrocyclic DKR of seco esters affords enantioenriched macrolactones. An optimized protocol (using Candida antarctica lipase B (~0.04 mol%) and Shvo’s catalyst) forms 14–19-membered macrocycles with excellent enantioselectivities (85–99% e.e.). A variety of macrolactones were synthesized including aliphatic macrocycles, meta- and paracyclophanes as well as a macrodiolide via a dimerization protocol that was converted to the natural product macrolide (−)-pyrenophorin. The dynamic kinetic resolution of secondary alcohols for the synthesis of macrocycles is reported. This approach uses a chemoenzymatic method to form enantioenriched 14–19-membered macrolactones and macrodiolides and can be used to prepare bioactive natural products.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1275-1282"},"PeriodicalIF":0.0,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510597","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

Efficient ethylene electrosynthesis by accelerating water dissociation 通过加速水解离实现高效乙烯电合成

Nature synthesis Pub Date : 2024-07-01 DOI: 10.1038/s44160-024-00593-7

Matthias M. Waegele

引用次数: 0

Biocatalytic desymmetrization for synthesis of chiral enones using flavoenzymes 利用黄酶类生物催化非对称性合成手性烯酮

Nature synthesis Pub Date : 2024-07-01 DOI: 10.1038/s44160-024-00596-4

Qing-Qing Zeng, Qian-Yi Zhou, Carla Calvó-Tusell, Shuang-Yu Dai, Xiang Zhao, Marc Garcia-Borràs, Zhen Liu

{"title":"Biocatalytic desymmetrization for synthesis of chiral enones using flavoenzymes","authors":"Qing-Qing Zeng, Qian-Yi Zhou, Carla Calvó-Tusell, Shuang-Yu Dai, Xiang Zhao, Marc Garcia-Borràs, Zhen Liu","doi":"10.1038/s44160-024-00596-4","DOIUrl":"10.1038/s44160-024-00596-4","url":null,"abstract":"Efficient methods for achieving desaturation of carbonyl compounds are highly sought after in organic chemistry. In contrast to synthetic approaches, enzymatic desaturation systems offer the potential to enhance sustainability and selectivity but have remained elusive. Here we report the development of an enzymatic desaturation system based on flavin-dependent ene-reductases for desymmetrizing cyclohexanones. This platform facilitates the synthesis of a wide array of chiral cyclohexenones bearing quaternary stereocentres—structural motifs commonly present in bioactive molecules—with excellent yields and enantioselectivities. Experimental and computational mechanistic studies reveal the roles of key active-site residues that enable the formation and stabilization of an enolate intermediate in the desaturation event. Additionally, by leveraging these insights, we have devised a biocatalytic strategy for the synthesis of enones by reductively desymmetrizing cyclohexadienones. This method yields the opposite enantiomer compared to our desaturation system, underscoring the enantiodivergence and broad applicability of our flavin-based desymmetrization approaches. Biocatalytic methods for the synthesis of chiral cyclohexenones bearing quaternary stereocentres through oxidation and reduction reactions are reported. Mechanistic studies reveal the role of active-site residues in the oxidation process and inform the development of the enzymatic reduction reaction.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 11","pages":"1340-1348"},"PeriodicalIF":0.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510614","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

Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer 六氟异丙醇辅助单电子转移选择性分子内合成杂环

Nature synthesis Pub Date : 2024-07-01 DOI: 10.1038/s44160-024-00566-w

Jiale Xie, Jiayu Zhang, Sitthichok Kasemthaveechok, Sara López-Resano, Eric Cots, Feliu Maseras, Mónica H. Pérez-Temprano

{"title":"Hexafluoroisopropanol-assisted selective intramolecular synthesis of heterocycles by single-electron transfer","authors":"Jiale Xie, Jiayu Zhang, Sitthichok Kasemthaveechok, Sara López-Resano, Eric Cots, Feliu Maseras, Mónica H. Pérez-Temprano","doi":"10.1038/s44160-024-00566-w","DOIUrl":"10.1038/s44160-024-00566-w","url":null,"abstract":"Intramolecular amination of remote aliphatic C–H bonds via hydrogen-atom transfer reactions has become a powerful tool for accessing saturated nitrogen-containing heterocycles. However, the formation of six-membered rings or oxa-heterocycles remains a formidable challenge for Hofmann–Löffler–Freytag reactions. Here we show how by simply combining bench-stable (bis(trifluoroacetoxy)iodo)benzene and hexafluoroisopropanol (HFIP) we can switch from the well-established Hofmann–Löffler–Freytag mechanism to a different versatile reaction pathway that enables selective C(sp3)–H bond functionalization. We have exploited the facile formation of radical cations via single-electron transfer, in the presence or absence of light, to synthesize pyrrolidines and piperidines, including drug-type molecules, along with O-heterocycles. Experimental and computational mechanistic studies support two distinct mechanistic pathways, depending on the electron density of the substrate, in which the HFIP plays a multifunctional role. Saturated heterocycles are prevalent motifs in organic synthesis but their synthesis still presents persistent challenges. Now, a hypervalent iodine(III)-mediated selective intramolecular C(sp3)–H functionalization, facilitated by hexafluoroisopropanol, is reported, which via single-electron transfer provides access to pyrrolidines, piperidines and O-heterocycles in the presence or absence of light.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 8","pages":"1021-1030"},"PeriodicalIF":0.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00566-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510600","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

Boryl radical-mediated halogen-atom transfer enables arylation of alkyl halides with electrophilic and nucleophilic coupling partners 硼烷基自由基介导的卤素原子转移使烷基卤化物与亲电和亲核偶联伙伴发生芳基化反应

Nature synthesis Pub Date : 2024-07-01 DOI: 10.1038/s44160-024-00587-5

Zhenhua Zhang, Michael J. Tilby, Daniele Leonori

{"title":"Boryl radical-mediated halogen-atom transfer enables arylation of alkyl halides with electrophilic and nucleophilic coupling partners","authors":"Zhenhua Zhang, Michael J. Tilby, Daniele Leonori","doi":"10.1038/s44160-024-00587-5","DOIUrl":"10.1038/s44160-024-00587-5","url":null,"abstract":"Traditional metal-catalysed cross-couplings of alkyl halides for C(sp3)–C(sp2) bond formation are often challenging to achieve. Processes where the alkyl halide is initially converted into a radical species can provide valuable complementarity. So far, these strategies are almost exclusively orchestrated by silicon-based reagents, which can be expensive, have low atom economy and are sensitive to steric factors. Here we report the use of the stable Lewis acid–Lewis base complex Me3N–BH3, which, upon conversion into its corresponding amine-ligated boryl radical, enables nickel- and copper-catalysed cross-coupling of alkyl iodides and bromides with electrophilic aryl bromides and nucleophilic aryl boronic acids. Mechanistically, this method uses the amine borane radical’s propensity to activate halides via halogen-atom transfer through highly polarized transition states. This reactivity features mild conditions and broad tolerability of functional groups and engages sterically hindered alkyl halides. The use of alkyl halides in radical cross-couplings generally requires silicon reagents as halogen abstractors. Now Me3N–BH3 is reported to facilitate these couplings with both aryl bromides and aryl boronic acids under either nickel or copper catalysis.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1221-1230"},"PeriodicalIF":0.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510613","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

Porous polycyclic aromatic heterocycles via metal-free annulative π-extension 通过无金属环状π-扩展实现多孔多环芳香杂环

Nature synthesis Pub Date : 2024-07-01 DOI: 10.1038/s44160-024-00590-w

Kalipada Koner, Rahul Banerjee

{"title":"Porous polycyclic aromatic heterocycles via metal-free annulative π-extension","authors":"Kalipada Koner, Rahul Banerjee","doi":"10.1038/s44160-024-00590-w","DOIUrl":"10.1038/s44160-024-00590-w","url":null,"abstract":"The synthesis of nitrogen-containing polycyclic aromatic heterocycles (PAHs) is important because of their expanding range of applications. Over the past decade, the preparation of PAHs has largely relied on complex, multistep processes. These methods necessitate the use of expensive transition-metal catalysts and sophisticated techniques. Here we report a one-pot, metal-free synthesis of PAHs that addresses the limits of traditional methods. Our method uses a sequence of imine condensation, nucleophilic aromatic substitution and intramolecular Friedel–Crafts reactions, leading to the synthesis of aromatic and seven-ring fused 5,11,17-triazatrinaphthylene compounds. The approach can incorporate various substituents, including alkyl chains and heteroatoms, with high regioselectivity and efficiency. In addition, this method enables the in situ crystallization of 5,11,17-triazatrinaphthylene molecules using precipitation under high pressure, potentially removing the need for chromatographic separation and allowing for bulk-scale production. This process is particularly beneficial for creating crystalline, porous polyaromatic heterocyclic materials with tunable permanent porosity. A one-pot, metal-free synthesis of nitrogen-containing polycyclic aromatic heterocycles is reported by using a sequence of imine condensation, nucleophilic aromatic substitution and intramolecular Friedel–Crafts reactions. Subsequently, in situ crystallization using precipitation under high pressure yields a series of substituted and unsubstituted 5,11,17-triazatrinaphthylene compounds.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 10","pages":"1266-1274"},"PeriodicalIF":0.0,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141510601","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

Boryl radicals facilitate C(sp2)–C(sp3) cross-coupling reactions 硼烷基促进 C（sp2）-C（sp3）交叉偶联反应

Nature synthesis Pub Date : 2024-07-01 DOI: 10.1038/s44160-024-00586-6

Jesus Rodrigalvarez, Ruben Martin

引用次数: 0