Nature synthesisPub Date : 2025-10-08DOI: 10.1038/s44160-025-00906-4
Eric J. Piechota
{"title":"Palladium makes agostic C–H bonds more acidic","authors":"Eric J. Piechota","doi":"10.1038/s44160-025-00906-4","DOIUrl":"10.1038/s44160-025-00906-4","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1174-1174"},"PeriodicalIF":20.0,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256850","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}
Nature synthesisPub Date : 2025-09-29DOI: 10.1038/s44160-025-00878-5
Zibo Bai, Tobias Ritter
{"title":"Applications of thianthrene chemistry in organic synthesis","authors":"Zibo Bai, Tobias Ritter","doi":"10.1038/s44160-025-00878-5","DOIUrl":"10.1038/s44160-025-00878-5","url":null,"abstract":"Thianthrene was first reported in 1869 and has been widely used in materials science for redox-flow batteries, polymers, supramolecular chemistry and phosphorescent materials. Despite extensive studies of the thianthrene radical cation and its reactivity since 1957, applications of thianthrene in synthetic chemistry were virtually absent from the literature until 2019. The then-discovered unusually high selectivity for thianthrenation by electrophilic aromatic substitution allowed for the synthesis of single constitutional isomers of structurally complex aryl-thianthrenium salts, which were mostly used as aryl (pseudo)halide analogues for subsequent functionalization. Since then, it has become apparent that the electronic structure of the thianthrenium substituent enables reaction chemistry that in part goes beyond what can be achieved with conventional organo(pseudo)halides. In this Review, we analyse and explain the fundamental aspects of organothianthrene chemistry, highlight the difference in reactivity to conventional organo(pseudo)halides and showcase its diverse applications. Thianthrene, long used in materials science, has recently emerged as a powerful reagent in organic synthesis. Its unique electronic structure enables access to diverse aryl, alkenyl and alkyl thianthrenium salts, which exhibit reactivity beyond conventional (pseudo)halides. This Review highlights the fundamental properties, distinctive reactivity and synthetic applications of these thianthrenium salts.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1187-1199"},"PeriodicalIF":20.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256853","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}
Nature synthesisPub Date : 2025-09-23DOI: 10.1038/s44160-025-00900-w
Peter W. Seavill
{"title":"Hydrogenation using ammonia-borane","authors":"Peter W. Seavill","doi":"10.1038/s44160-025-00900-w","DOIUrl":"10.1038/s44160-025-00900-w","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1171-1171"},"PeriodicalIF":20.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256843","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}
Nature synthesisPub Date : 2025-09-23DOI: 10.1038/s44160-025-00901-9
Jet-Sing M. Lee
{"title":"Global aromaticity at the macrocyclic size limit","authors":"Jet-Sing M. Lee","doi":"10.1038/s44160-025-00901-9","DOIUrl":"10.1038/s44160-025-00901-9","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1173-1173"},"PeriodicalIF":20.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256858","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}
Nature synthesisPub Date : 2025-09-16DOI: 10.1038/s44160-025-00879-4
Jing Li, Xiang Liu, Si-Min Xu, Ming Xu, Yunlong Wang, Yizheng Lyu, An-Zhen Li, Ye Wang, Xi Wang, Tiancong Zhou, Hua Zhou, Yue Peng, Xuning Li, Lirong Zheng, Haohong Duan
{"title":"Sustainable oxime production via the electrosynthesis of hydroxylamine in a free state","authors":"Jing Li, Xiang Liu, Si-Min Xu, Ming Xu, Yunlong Wang, Yizheng Lyu, An-Zhen Li, Ye Wang, Xi Wang, Tiancong Zhou, Hua Zhou, Yue Peng, Xuning Li, Lirong Zheng, Haohong Duan","doi":"10.1038/s44160-025-00879-4","DOIUrl":"https://doi.org/10.1038/s44160-025-00879-4","url":null,"abstract":"<p>Hydroxylamine (NH<sub>2</sub>OH) is an important feedstock for oxime production. Coreduction of NO<sub><i>x</i></sub> and aldehydes or ketones enables sustainable one-step oximation by utilizing in situ *NH<sub>2</sub>OH intermediates but suffers from side reactions and reduced current density due to the presence of multiple reactants in one reactor. Here we decouple oximation into two steps, the electrochemical synthesis of free NH<sub>2</sub>OH via nitrite (NO<sub>2</sub><sup>−</sup>) electroreduction and the aldehyde or ketone oximation chemical step, circumventing the negative effects (such as site blocking, aldehyde or ketone electroreduction, or crossover) encountered in one-step oximation. By using a Ketjen-black-supported iron phthalocyanine as the catalyst, we achieve an exceptionally high partial current density of free NH<sub>2</sub>OH (<i>j</i><sub>NH2OH</sub>) of 262.9 mA cm<sup>−2</sup> (corresponding to productivity of 2.452 mmol cm<sup>−2</sup> h<sup>−1</sup>) in neutral conditions at an industrially relevant current density of 500 mA cm<sup>−2</sup>. By coupling NH<sub>2</sub>OH electrosynthesis with subsequent oximation in two steps, nearly stoichiometric oximes are produced with high efficiency and broad applicability. This work paves the way toward a sustainable oxime industry.</p><figure></figure>","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073040","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}
Nature synthesisPub Date : 2025-09-16DOI: 10.1038/s44160-025-00874-9
John A. Kelly, Arseni Kostenko, Shigeyoshi Inoue
{"title":"Direct access to a neutral alumene via CO reduction by a dialane and further CO homologation","authors":"John A. Kelly, Arseni Kostenko, Shigeyoshi Inoue","doi":"10.1038/s44160-025-00874-9","DOIUrl":"https://doi.org/10.1038/s44160-025-00874-9","url":null,"abstract":"<p>Multiple bonds between heavy elements have been shown to be not only stable but also offer divergent reactivity. Accordingly, there has been a drive in research to isolate such species. Here we report on the synthesis of a compound containing an aluminium–carbon double bond (alumene). The alumene was formed by exposing a dialane to a CO atmosphere. Experimental data and quantum chemical calculations confirm the existence of a <i>π</i>-bond between the aluminium and carbon centre. The mechanism for the formation of the alumene was calculated and indicated a heterocyclic intermediate, which we were able to observe spectroscopically. Treating the alumene with excess CO leads to CO homologation, forming a C<sub>3</sub>O<sub>2</sub> chain initiated by interaction of a CO molecule with the <i>π</i>-bond of Al=C.</p><figure></figure>","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"9 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073041","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}
Nature synthesisPub Date : 2025-09-16DOI: 10.1038/s44160-025-00883-8
Liang Hu, Jie-Lun Yan, Yu-Kun Lin, Daniel A. Strassfeld, Jin-Quan Yu
{"title":"Regiocontrollable [2 + 2] benzannulation of γ,δ-C(sp3)–H bonds with dihaloarenes using palladium catalysis","authors":"Liang Hu, Jie-Lun Yan, Yu-Kun Lin, Daniel A. Strassfeld, Jin-Quan Yu","doi":"10.1038/s44160-025-00883-8","DOIUrl":"https://doi.org/10.1038/s44160-025-00883-8","url":null,"abstract":"<p>Methylene-selective C–H functionalization at distal positions is a challenge in the field of Pd(II) catalysis. We have previously reported a ligand-enabled β,γ-C–H coupling with dihaloarenes for the synthesis of benzocyclobutenes (BCBs) as a promising class of scaffolds in drug discovery. Here we report a Pd(II)-catalysed method for the γ,δ-methylene C–H activation of free aliphatic acids and subsequent coupling with dihaloarenes, which offers an efficient route for the synthesis of diversely functionalized BCBs. The development of a carboxyl-pyridone ligand is crucial for the remote C(<i>sp</i><sup>3</sup>)–H activation. Notably, previous γ,δ-methylene C–H activation reactions of monoaliphatic acids are limited to carbocyclic substrates. The site-selective activation of γ,δ-C–H bonds installs the BCB pharmacophores that are one carbon atom further away from the carboxyl group than in previous studies. Given the carboxyl group can serve as hydrogen-bond donor or acceptor, such alternation of distance between two interactions can impact bioactivity.</p><figure></figure>","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"81 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073050","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}
Nature synthesisPub Date : 2025-09-11DOI: 10.1038/s44160-025-00893-6
{"title":"The synthesis of perovskites","authors":"","doi":"10.1038/s44160-025-00893-6","DOIUrl":"10.1038/s44160-025-00893-6","url":null,"abstract":"In this Focus issue, we examine synthetic routes to perovskites for a variety of applications.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1019-1019"},"PeriodicalIF":20.0,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00893-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145073042","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}