Nature synthesis最新文献_第4页

Electrochemical etherification and amination 电化学醚化和胺化

Nature synthesis Pub Date : 2024-10-25 DOI: 10.1038/s44160-024-00684-5

Peter W. Seavill

引用次数: 0

Multisite modifications of arenes using ketones as removable handles enabled by Pd and norbornene cooperative catalysis

Nature synthesis Pub Date : 2024-10-25 DOI: 10.1038/s44160-024-00673-8

Kai-Liang Tao, Xing Wang, Huan Liu, Wen-Qing Chen, Yi Sun, Yun-Qian Zhang, Yu-Xi Li, Zhen-Yu Wang, Yang Ye, Hui Xu, Lefu Lan, Hui-Xiong Dai

{"title":"Multisite modifications of arenes using ketones as removable handles enabled by Pd and norbornene cooperative catalysis","authors":"Kai-Liang Tao, Xing Wang, Huan Liu, Wen-Qing Chen, Yi Sun, Yun-Qian Zhang, Yu-Xi Li, Zhen-Yu Wang, Yang Ye, Hui Xu, Lefu Lan, Hui-Xiong Dai","doi":"10.1038/s44160-024-00673-8","DOIUrl":"10.1038/s44160-024-00673-8","url":null,"abstract":"Natural products serve as crucial sources for new drugs and play an indispensable role in drug discovery. Late-stage functionalization of natural products is an efficient method for diversifying their structures, fine-tuning their biological properties and rapidly constructing molecular libraries. Polysubstituted arenes serve as structural cores in pharmaceuticals derived from natural products. However, programmable multisite arene modification remains a largely unmet challenge. Here, using commercially available and easy-to-synthesize aryl ketones as substrates, we present the programmable multifunctionalization of natural products via a palladium- and norbornene-catalysed Catellani-type reaction. Given the ease of installing an acyl group and using it as a relay, this protocol enables the incorporation of a variety of bioactive molecules into natural products via successive acylation and deacylation processes. Furthermore, this strategy was applied to the construction of a molecular library based on dehydroabietic acid. Multiple molecules with substantially increased activity were obtained through antimicrobial activity screening. Polysubstituted arenes are ubiquitous structural cores in natural products and drugs but their synthesis through programmable arene modification remains a challenge. Now, a palladium- and norbornene-catalysed Catellani-type reaction of aryl ketones, through successive acylation and deacylation, allows the synthesis of polysubstituted arenes.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"209-218"},"PeriodicalIF":0.0,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397416","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

Predicting enantioselectivity for diverse substrates 预测不同底物的对映选择性

Nature synthesis Pub Date : 2024-10-25 DOI: 10.1038/s44160-024-00683-6

Alison Stoddart

引用次数: 0

Reshaping amino acids 重塑氨基酸

Nature synthesis Pub Date : 2024-10-23 DOI: 10.1038/s44160-024-00676-5

Jingyang Qin, Christopher J. Teskey

引用次数: 0

Polyhedral expansion of closo-hexaboranes 闭己硼烷的多面体扩展

Nature synthesis Pub Date : 2024-10-21 DOI: 10.1038/s44160-024-00680-9

Alexandra R. Groves

引用次数: 0

Designing highly delocalized solitons by harnessing the structural parity of π-conjugated polymers

Nature synthesis Pub Date : 2024-10-16 DOI: 10.1038/s44160-024-00665-8

Kalyan Biswas, Jesús Janeiro, Aurelio Gallardo, Marco Lozano, Ana Barragán, Berta Álvarez, Diego Soler-Polo, Oleksandr Stetsovych, Andrés Pinar Solé, Koen Lauwaet, José M. Gallego, Dolores Pérez, Rodolfo Miranda, José I. Urgel, Pavel Jelínek, Diego Peña, David Écija

{"title":"Designing highly delocalized solitons by harnessing the structural parity of π-conjugated polymers","authors":"Kalyan Biswas, Jesús Janeiro, Aurelio Gallardo, Marco Lozano, Ana Barragán, Berta Álvarez, Diego Soler-Polo, Oleksandr Stetsovych, Andrés Pinar Solé, Koen Lauwaet, José M. Gallego, Dolores Pérez, Rodolfo Miranda, José I. Urgel, Pavel Jelínek, Diego Peña, David Écija","doi":"10.1038/s44160-024-00665-8","DOIUrl":"10.1038/s44160-024-00665-8","url":null,"abstract":"π-Conjugated polymers are a class of materials featuring an alternation of single and double bonds along their backbone, a configuration that can result in delocalized π-electrons. The unique electronic structure of these polymers makes them vital in applications such as organic electronics, solar cells and light-emitting diodes. A key feature in such materials is the emergence of topological quasiparticles, termed solitons, which are crucial for their observed high electrical conductivity. By using on-surface synthesis, we present a chemical reaction based on the regio- and stereoselective coupling of indenyl moieties for fabricating π-conjugated acenoindenylidene polymers, which feature a longitudinal polyacetylene backbone, on a Au(111) surface. The relationship between structural parity and electronic properties is investigated. We discover that odd-membered polymers exhibit an in-gap soliton state, which, due to their low bandgaps, spatially extends several nanometres along the longitudinal polyacetylene backbone. Our findings pave the way for the design of π-conjugated polymers that are able to host intrinsic solitons through chemical design by exploiting structural parity, without the need for external doping. An on-surface synthetic route for the regio- and stereoselective coupling of indenyl moieties, affording the design of π-conjugated acenoindenylidene polymers on Au(111), is reported. The relationship between the structural parity of the polymers and their electronic properties reveals the emergence of highly delocalized soliton quasiparticles in odd-membered polymers.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"233-242"},"PeriodicalIF":0.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397419","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

Reproducibility in automated chemistry laboratories using computer science abstractions 利用计算机科学抽象技术实现自动化化学实验室的可重复性

Nature synthesis Pub Date : 2024-10-10 DOI: 10.1038/s44160-024-00649-8

Richard B. Canty, Milad Abolhasani

{"title":"Reproducibility in automated chemistry laboratories using computer science abstractions","authors":"Richard B. Canty, Milad Abolhasani","doi":"10.1038/s44160-024-00649-8","DOIUrl":"10.1038/s44160-024-00649-8","url":null,"abstract":"While abstraction is critical for the transferability of automated laboratory science in (bio)chemical and materials sciences, its improper implementation is a technical debt taken against the reproducibility of experimental results. Over the decades, computer science has developed guidelines and strategies for how abstractions are captured in programming languages—particularly concerning the substitutability of implementations of abstracted ideas and the clear definition of the contexts in which abstractions are used. However, few programming languages developed for automated experiments fully leverage the wisdom learned in computer science. To achieve collaborative sharing of scientific knowledge via automated laboratories, the way that experimental protocols are codified and interpreted by machine agents must use abstractions responsibly and with reproducibility, rather than solely transferability, at its core. This Review discusses how computer science principles of abstraction can be translated to create more reproducible automation as an enabler for the acceleration of collaborative research with self-driving laboratories. Digital workflow representations in automated and autonomous chemistry laboratories can achieve transferability by using abstract concepts. However, such abstractions must abide by certain rules to ensure reproducibility. Lessons learned from computer science for responsible abstraction are translated into an automated chemistry laboratory context to guide digital workflow development towards reproducibility.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"3 11","pages":"1327-1339"},"PeriodicalIF":0.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142596131","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

Photocatalytic site-selective radical C(sp3)–H aminoalkylation, alkylation and arylation of silanes

Nature synthesis Pub Date : 2024-10-10 DOI: 10.1038/s44160-024-00664-9

Xingyi He, Yizhi Zhang, Shanshan Liu, Weilu Zhang, Zhening Liu, Yunlong Zhao, Xiao Shen

{"title":"Photocatalytic site-selective radical C(sp3)–H aminoalkylation, alkylation and arylation of silanes","authors":"Xingyi He, Yizhi Zhang, Shanshan Liu, Weilu Zhang, Zhening Liu, Yunlong Zhao, Xiao Shen","doi":"10.1038/s44160-024-00664-9","DOIUrl":"10.1038/s44160-024-00664-9","url":null,"abstract":"Organosilicon compounds are of great value in chemistry and material science. However, site-selective C–H bond functionalization of simple silanes to prepare more complex organosilicon compounds is challenging because of the presence of multiple C–H bonds in the same molecule. Here we report a broadly applicable photocatalytic site-selective radical functionalization of organosilicon compounds enabled by the β-silicon effect, wherein a silyl group selectively activates β-C(sp3)–H bonds, leading to lower bond dissociation energy than that of α-C(sp3)–H bonds and γ-C(sp3)–H bonds. Various β-C(sp3)–H bond aminoalkylation, alkylation and arylation reactions have been achieved and applied in complex molecule synthesis. Site-selective C–H functionalization of silanes is challenging because of the presence of multiple C–H bonds in the same molecule. Now a general photocatalytic site-selective radical functionalization of organosilicon compounds is reported, enabled by the β-silicon effect, which activates β-C(sp3)–H bonds. These reactions are applicable to linear and complex cyclic silanes.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"188-195"},"PeriodicalIF":0.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397435","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

Method for the β-selective radical C(sp3)–H functionalization of silanes

Nature synthesis Pub Date : 2024-10-10 DOI: 10.1038/s44160-024-00675-6

引用次数: 0

Mechanochemical nitrogen fixation catalysed by molybdenum complexes

Nature synthesis Pub Date : 2024-10-09 DOI: 10.1038/s44160-024-00661-y

Shun Suginome, Kurumi Murota, Akira Yamamoto, Hisao Yoshida, Yoshiaki Nishibayashi

{"title":"Mechanochemical nitrogen fixation catalysed by molybdenum complexes","authors":"Shun Suginome, Kurumi Murota, Akira Yamamoto, Hisao Yoshida, Yoshiaki Nishibayashi","doi":"10.1038/s44160-024-00661-y","DOIUrl":"10.1038/s44160-024-00661-y","url":null,"abstract":"Transition metal-catalysed mechanochemical reactions using ball milling have emerged as important tools to realize unique organic transformations. Mechanochemical reactions have advantages over conventional homogeneous reactions, such as using a small amount of organic solvent, having a broad substrate scope and being generally fast and selective reactions. An increasing number of mechanochemical reactions between solid substrates have been examined, but only a few examples of mechanochemical reactions involving gaseous substrates, such as nitrogen fixation to convert dinitrogen into ammonia, have been reported until now. Here we develop catalytic mechanochemical nitrogen fixation using molybdenum complexes as molecular catalysts. An atmospheric pressure of dinitrogen was reacted with samarium diiodide as a reductant and water or alcohols as proton sources in the presence of the molybdenum catalysts, using ball milling under solvent-free and near-ambient reaction conditions to afford up to 860 equivalents of ammonia based on the catalyst. In addition, we demonstrated that even insoluble cellulose can be applied as the proton source. Further, we revealed that the molybdenum-catalysed mechanochemical nitrogen fixation proceeds via nitrogen–nitrogen bond cleavage at the gas–solid interface and nitrogen–hydrogen bond formation in the solid phase. The use of large amounts of solvents is an obstacle to the practical application of nitrogen fixation using transition metal complexes. Here catalytic ammonia synthesis is achieved by reacting dinitrogen (1 atm) with samarium diiodide and proton sources, including cellulose, in the presence of molybdenum catalysts under solvent-free ball-milling conditions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 2","pages":"243-251"},"PeriodicalIF":0.0,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s44160-024-00661-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143397432","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