RSC Mechanochemistry最新文献

{"title":"Mechanochemistry enabled highly efficient solvent-free deoxygenation of phosphine oxides in air†","authors":"Koji Kubota, Reon Hisazumi, Tamae Seo and Hajime Ito","doi":"10.1039/D4MR00011K","DOIUrl":"https://doi.org/10.1039/D4MR00011K","url":null,"abstract":"<p >Deoxygenation of phosphine oxides is an important method for the synthesis of valuable organophosphine compounds and recycling of phosphorus resources. However, existing solution-based deoxygenation protocols usually require long reaction times, significant amounts of potentially harmful organic solvents, and inert gas atmospheres. In addition, reactions of poorly soluble phosphine oxides are challenging and often inefficient. Herein, we demonstrate that a high-temperature mechanochemical protocol enables the highly efficient solvent-free deoxygenation of phosphine oxides with hydrosilanes in the presence of a phosphoric acid additive. These reactions were rapid and completed within 30 min for most substrates. Notably, this is the first practical deoxygenation of phosphine oxides in which all synthetic operations can be carried out in air. A preliminary study on the mechanochemical catalytic Wittig reaction is also described.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00011k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583709","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}

{"title":"Unprecedented linear products by a mechanochemically activated Biginelli reaction using lawsone†","authors":"Christina L. Koumpoura, Laure Vendier, Christian Bijani, Anne Robert, Philippe Carbonnière, Jean-Marc Sotiropoulos and Michel Baltas","doi":"10.1039/D3MR00032J","DOIUrl":"https://doi.org/10.1039/D3MR00032J","url":null,"abstract":"<p >The Biginelli reaction, a crucial multicomponent reaction, was investigated involving 2-hydroxy-1,4-naphthoquinone (lawsone), <em>p</em>-substituted benzaldehydes, and ureas. Surprisingly, the classic Biginelli cyclized DHPM was not observed under various experimental conditions. Mechanochemical conditions, unlike traditional liquid phase conditions, led to the unprecedented formation of a series of ‘Biginelli-linear’ lawsone derivatives with high yields. The observed outcomes were consistent with DFT theoretical predictions, highlighting the preference for the Michael adduct under liquid conditions and the energetically implausible cyclization pathway for the classic DHPM compound. Additionally, the study achieved the novel cyclization of a ‘Biginelli-linear’ lawsone derivative into a cyclic carbamate for the first time.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d3mr00032j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140924786","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}

{"title":"Synthesis of short DNA and RNA fragments by resonant acoustic mixing (RAM)†","authors":"James D. Thorpe, Julian Marlyn, Stefan G. Koenig and Masad J. Damha","doi":"10.1039/D4MR00009A","DOIUrl":"https://doi.org/10.1039/D4MR00009A","url":null,"abstract":"<p >We demonstrate the first use of Resonant Acoustic Mixing (RAM) without bulk solvent for the synthesis of short oligonucleotide fragments. Using the modified H-phosphonate approach, DNA, RNA, and 2′-modified nucleotides were successfully coupled to 3′-protected nucleosides in high yields (63–92%) while reducing solvent volume by 90%. In addition to synthesizing protected phosphodiester (PO) dimers and trimers, we also synthesized protected phosphorothioate (PS) dimers in good yields (63–65%). Using phosphoramidite chemistry, we were similarly able to reduce the solvent volume by 90% while coupling DNA phosphoramidites (58–92%) and RNA phosphoramidites (55–95%) with 3′-protected nucleosides in high yields followed by traditional oxidation with iodine in solution. Both strategies were successfully scaled up to multi-gram quantities which was facilitated by the use of RAM, offering the potential for larger scale-up, up to hundreds of kilograms continuously.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00009a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583708","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}

{"title":"Grinding and the anisotropic environment: influences on the diastereoselective formation of Group 15 allyl complexes†","authors":"Lauren E. Wenger and Timothy P. Hanusa","doi":"10.1039/D4MR00001C","DOIUrl":"https://doi.org/10.1039/D4MR00001C","url":null,"abstract":"<p >The heavy Group 15 allyls <img> (E = As, Sb, Bi; [A′] = [1,3-(SiMe<small>₃</small>)<small>₂</small>C<small>₃</small>H<small>₃</small>]<small>⁻</small>) can be prepared either in solution or mechanochemically, and exist in two diastereomeric forms of C<small>₁</small> and C<small>₃</small> symmetry. For E = As and Sb, their ratio varies with the method of preparation: the C<small>₁</small> diastereomer is the major form by both methods, but the mechanochemical route increases the C<small>₁</small> : C<small>₃</small> ratio compared to synthesis in hexanes solution. The difference in selectivity has previously been identified as a consequence of the layered crystal lattices of the EX<small>₃</small> reagents, which provide a templating effect through an anisotropic grinding environment. How this selectivity changes with other typical mechanochemical variables is explored here, including the use of different reagents and LAG solvents, pre-grinding the reagents, the use of different milling media (stainless steel, Teflon, <em>etc.</em>) and apparatus (mixer mill, planetary mill), and the number and size of balls. The extent to which the anisotropic environment is either maintained or modified during synthesis (especially by LAG and the choice of metal reagent) affects the diastereomeric ratio.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00001c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141583707","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}

{"title":"Protecting-group-free mechanosynthesis of amides from hydroxycarboxylic acids: application to the synthesis of imatinib†","authors":"Tatsiana Nikonovich, Tatsiana Jarg, Jevgenija Martõnova, Artjom Kudrjašov, Danylo Merzhyievskyi, Marina Kudrjašova, Fabrice Gallou, Riina Aav and Dzmitry Kananovich","doi":"10.1039/D4MR00006D","DOIUrl":"https://doi.org/10.1039/D4MR00006D","url":null,"abstract":"<p >Despite considerable advancements in mechanochemical amide couplings, there is a paucity of studies addressing chemoselective issues in these transformations, such as the tolerance of unmasked hydroxyl groups. In view of the high practical significance of amide coupling reactions in the synthesis of active pharmaceutical ingredients (APIs), we aimed to investigate the tolerance of unprotected hydroxyls in carboxylic acids towards various reported mechanochemical amide coupling conditions. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl) in combination with ethyl acetate as a liquid-assisted grinding (LAG) additive was revealed as the most selective amide coupling system that delivers 76–94% yields of amides from a range of hydroxycarboxylic acids, including <em>N</em>-Boc-protected amino acids serine and tyrosine. The EDC-mediated amide coupling protocol was employed in the synthesis of imatinib, an anticancer drug included in the World Health Organization's List of Essential Medicines. The target API was synthesized in an overall 86% yield and 99% HPLC purity through a two-step mechanochemical C–N bond assembling reaction sequence starting from 4-(hydroxymethyl)benzoic acid.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00006d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140924789","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}

{"title":"Introducing RSC Mechanochemistry","authors":"James D. Batteas and Tomislav Friščić","doi":"10.1039/D4MR90001D","DOIUrl":"https://doi.org/10.1039/D4MR90001D","url":null,"abstract":"<p >A graphical abstract is available for this content</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr90001d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140114121","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}

{"title":"Operando exploration of tribochemical decomposition in synthetic FeS2 thin film and mineral iron pyrite†","authors":"E. Muñoz-Cortés, J. Sánchez-Prieto, B. Zabala, C. Sanchez, E. Flores, A. Flores, E. Roman, J. R. Ares and R. Nevshupa","doi":"10.1039/D3MR00027C","DOIUrl":"https://doi.org/10.1039/D3MR00027C","url":null,"abstract":"<p >Tribochemical decomposition of thin-film synthetic iron disulfide and mineral iron pyrite was studied using a combination of <em>operando</em> mass-spectrometry coupled to ultrahigh vacuum tribochemical cell and the gas expansion system. The composition and kinetics of gas emission were analyzed using an original methodology. It was found that carbon-containing gases were dominating. The sulfur-containing gases comprised H<small>₂</small>S, COS and CS<small>₂</small>. The latter two were unexpected. The emission of these gases was traced back to solid-state chemical reactions kinetically controlled by the precursor concentrations and driven through non-thermal mechanisms, which we tentatively assigned to formation of sulfur radicals.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d3mr00027c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140924790","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}

{"title":"Mechanically induced self-propagating reactions (MSRs) to instantly prepare binary metal chalcogenides: assessing the influence of particle size, bulk modulus, reagents melting temperature difference and thermodynamic constants on the ignition time†","authors":"Matej Baláž, Róbert Džunda, Radovan Bureš, Tibor Sopčák and Tamás Csanádi","doi":"10.1039/D3MR00001J","DOIUrl":"https://doi.org/10.1039/D3MR00001J","url":null,"abstract":"<p >Mechanically induced self-propagating reactions (MSRs) offer the possibility to obtain desired products in an ultrafast and thus cost- and energy-efficient manner. In this work, this is demonstrated for ten binary metal chalcogenides (CdS, CdSe, In<small>₂</small>S<small>₃</small>, NiS, NiSe, PbS, PbSe SnSe, ZnS and ZnSe) by processing mixtures of metals and chalcogens in a planetary ball mill for less than 10 minutes. The MSR process for Ni-based systems is reported for the first time. The studied metals reacted much faster with selenium than with sulfur (with the exception of Ni). The successful MSR occurrence was evidenced by an abrupt increase of gas pressure in the milling jar monitored <em>in situ</em> and subsequently <em>ex situ</em> by X-ray diffraction. The crystallite size of the as-received products was usually in the range 40–260 nm. All the reactions were performed in an air atmosphere, and thus the presence of an inert gas was not necessary. An effort was made to correlate the observed ignition times with the particle size of the precursors, their melting temperature, bulk modulus and thermodynamic parameters (Δ<em>H</em>/<em>C</em><small>_p</small> and Δ<em>G</em>). While the thermodynamics does not seem to play an important role here, the particle size and bulk modulus of the reacting metal most probably influence the ignition time of MSRs. Namely, higher ductility (low bulk modulus) and finer particles seem to shorten the activation period before the MSR ignition. This study forms a cornerstone for further research in MSRs of metal chalcogenides because it universally assesses the influence of more parameters on the MSR course under fixed milling conditions for different systems. The proposed synthetic pathway also represents an improvement by reducing both time and energy by showing the possibility to reach some of the desired products within a minute-range, being much faster than a classical gradual reaction and further underlines the environmentally benign character of mechanochemistry.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d3mr00001j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140114122","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}

{"title":"Mechanochemical indium(0)-mediated Barbier allylation of carbonyl compounds: unexpected immiscible water additive effect for hydrophobic reagents†","authors":"Nuri Kim, Eun Sul Go and Jeung Gon Kim","doi":"10.1039/D4MR00005F","DOIUrl":"https://doi.org/10.1039/D4MR00005F","url":null,"abstract":"<p >Indium-mediated Barbier allylation exhibited a positive effect with the addition of water under mechanochemical ball-milling conditions. A small amount of water as an additive selectively boosted the allylation of solid-state hydrophobic aldehydes despite their immiscibility. The broad scope and scalability of this method are also demonstrated herein.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d4mr00005f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140924784","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}

{"title":"Kinetics of primary mechanochemical covalent-bond-forming reactions","authors":"Yerzhan S. Zholdassov, Ryan W. Kwok, Milan A. Shlain, Monil Patel, Mateusz Marianski and Adam B. Braunschweig","doi":"10.1039/D3MR00018D","DOIUrl":"https://doi.org/10.1039/D3MR00018D","url":null,"abstract":"<p >Mechanical activation of reactions can reduce significantly the amounts of solvent and energy required to form covalent organic bonds. Despite growing interest in the field of mechanochemistry and increasing reports of mechanochemical synthesis of organic molecules, the fundamental question of how stresses activate covalent-bond-forming (CBF) reactions remains unresolved. This question remains unresolved because of the difficulties involved in measuring the applied forces and the reaction times in mechanochemical reactors, and the challenges related to deconvoluting microscopic (primary) and macroscopic (secondary) processes in the analysis of reaction kinetics. Here we discuss the use nanoscopic probe-microscope tips to explore the kinetics of CBF reactions. Because these experiments examine reactions on monolayers, surfaces, or nanoscopic particles, they circumvent secondary processes to isolate how stress affects the rates of the primary, CBF events. The major result of these studies is an emerging consensus that stress accelerates reactions by distorting organic molecules and in doing so, lowers reaction activation energies and alters reaction trajectories. This new understanding of how stresses activate reactions can be used to predict the outcomes of CBF mechanochemical reactions, which will lead to the wider adoption of sustainable mechanochemical processes by the synthetic community.</p>","PeriodicalId":101140,"journal":{"name":"RSC Mechanochemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/mr/d3mr00018d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140114128","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}