Green Chemistry最新文献

{"title":"anti-Dihydroxylation of olefins enabled by in situ generated peroxyacetic acid†","authors":"Michael Tapera ,&nbsp;Mohit Chotia ,&nbsp;Jan Lukas Mayer-Figge ,&nbsp;Adrián Gómez-Suárez ,&nbsp;Stefan F. Kirsch","doi":"10.1039/d4gc03540b","DOIUrl":"10.1039/d4gc03540b","url":null,"abstract":"<div><div>Herein, we report a general and green protocol for the <em>anti</em>-dihydroxylation of unactivated alkenes. Combining H₂O₂ and acetic acid at 50 °C results in the formation of peroxyacetic acid, which enables the efficient synthesis of a wide range of <em>anti</em> 1,2-diols in moderate to good yields without the need for hazardous solvents or expensive transition metals as catalysts.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc03540b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"General electron–donor–acceptor complex mediated thioesterification reaction via site-selective C–H functionalization using aryl sulfonium Salts†","authors":"Roshan I. Patel ,&nbsp;Barakha Saxena ,&nbsp;Anuj Sharma","doi":"10.1039/d4gc03768e","DOIUrl":"10.1039/d4gc03768e","url":null,"abstract":"<div><div>Contemporary methods for synthesizing thioesters often necessitate expensive catalysts and harsh conditions, making their synthesis from chemical feedstocks challenging. Herein, we report a sustainable metal-, photocatalyst-, and oxidant-free electron donor–acceptor (EDA) mediated synthesis of thioesters <em>via</em> site-selective C–H functionalization using aryl sulfonium salts (acceptor) with potassium thioacid salts (donor) under visible light irradiation. Our approach enables rapid access to thioesters from a wide variety of arenes, including pharmaceutical and agrochemical compounds, as well as a diverse range of alkyl, aryl, and heteroaryl potassium thioacid salts with excellent efficiency and regioselectivity. Mechanistic studies supported the formation of an EDA-complex, and radical trapping experiments corroborated the involvement of a radical-based mechanism for the product formation. Moreover, our method demonstrates excellent atom economy and <em>E</em>-factor scores, which are considered excellent in terms of safety, economic and ecological yardsticks.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Acid-catalyzed regioselective remote heteroarylation of alkenes via CC bond migration†","authors":"Shengxiang Qin ,&nbsp;Yaqi Zhang ,&nbsp;Long Jiang ,&nbsp;Man Kin Tse ,&nbsp;Albert S. C. Chan ,&nbsp;Liqin Qiu","doi":"10.1039/d4gc03356f","DOIUrl":"10.1039/d4gc03356f","url":null,"abstract":"<div><div>We report herein the acid-catalyzed regioselective remote heteroarylation and reductive alkylation of alkenes. Various alkenes, including mono-, di-, and tri-substituted alkenes and cyclic alkenes, are applicable to this reaction. This method exhibits broad substrate scope, high functional group tolerance and high atomic economy. In addition, both gram-scale synthesis and product transformations demonstrate the potential utility of this reaction. It also provides an efficient and novel pathway to establish the valuable framework of 1,1-diaryl alkanes. Further mechanistic studies suggested that TfOH <em>in situ</em> generated by Cu(OTf)₂ and trace H₂O catalyzed the alkene migration. Then, heteroarylation was conducted by Friedel–Crafts type alkylation.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195752","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A comparative life cycle assessment of the synthesis of mesoporous silica materials on a small and a large scale†","authors":"Jose Vicente Ros-Lis ,&nbsp;Sylvia Vetter ,&nbsp;Pete Smith","doi":"10.1039/d4gc02347a","DOIUrl":"10.1039/d4gc02347a","url":null,"abstract":"<div><div>Silica mesoporous materials have been the subject of wide scientific interest with various applications. However, the environmental impacts associated with their preparation have scarcely been studied. In the present work, we applied the Life Cycle Assessment (LCA) methodology to the materials MCM-41, MCM-48, UVM-7, mesoporous Stober particles, SBA-15, SBA-16, HMS, KIT-5, KIT-6, MSU, FDU, nano-MCM-41 and nano-MCM-48 for small- (grams) and large-scale (several kilograms) production. Furthermore, various improvements are proposed, and the impact associated with each of them is quantified. The results show that the values of a single score, a normalized and weighed combination of the damage categories, and net greenhouse gas emissions (NGHGE) are highly dependent on the synthesis procedures. On a small scale, the main impact is due to the use of energy and solvents. By contrast on a large scale, the use of solvents, tetraethylorthosilicate and the structure directing agent are the main determinants. From the values obtained for the different materials and scenarios, we estimate that the preparation of this class of materials could have an NGHGE of 54 ± 30 and 31 ± 18 kg CO₂ eq. per kg of mesoporous material for small- and large-scale production, respectively. The use of calcination <em>versus</em> extraction, the incorporation of renewable energy and distillation/rectification are initiatives that can contribute to a significant reduction of the environmental impact.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc02347a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141946921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bioprocess development and scale-up for cis,cis-muconic acid production from glucose and xylose by Pseudomonas putida†","authors":"Sekgetho C. Mokwatlo ,&nbsp;Bruno C. Klein ,&nbsp;Pahola Thathiana Benavides ,&nbsp;Eric C. D. Tan ,&nbsp;Colin M. Kneucker ,&nbsp;Chen Ling ,&nbsp;Christine A. Singer ,&nbsp;Robert Lyons ,&nbsp;Violeta Sànchez i Nogué ,&nbsp;Kelley V. Hestmark ,&nbsp;Morgan A. Ingraham ,&nbsp;Kelsey J. Ramirez ,&nbsp;Christopher W. Johnson ,&nbsp;Gregg T. Beckham ,&nbsp;Davinia Salvachúa","doi":"10.1039/d4gc03424d","DOIUrl":"10.1039/d4gc03424d","url":null,"abstract":"<div><div> <em>cis</em>,<em>cis</em>-Muconic acid (MA) is a bio-based chemical that can be converted to direct replacement chemicals or performance-advantaged bioproducts. We recently engineered the bacterium <em>Pseudomonas putida</em> KT2440 for the co-utilization of glucose and xylose to produce MA. This study evaluates the effect of additional genetic modifications, media composition, and bioprocess strategy on MA titer, productivity, and yield in bioreactor cultivations. We achieve a MA titer of 47.2 g L⁻¹, a productivity of 0.49 g L⁻¹ h⁻¹, and a yield of 0.50 C-mol C-mol⁻¹ from glucose and xylose supplemented with 5% (v/v) corn steep liquor with a <em>P. putida</em> strain harboring the deletion of <em>gacS</em>. Additionally, we demonstrate efficient MA production from corn stover-derived sugars and scalability to 150 L bioreactors. Techno-economic analysis and life cycle assessment predict that adipic acid, derived from catalytic hydrogenation of MA, can achieve a selling price as low as $2.60 per kg, approaching cost parity and reducing greenhouse gas emissions by up to 80% relative to fossil carbon-based adipic acid.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc03424d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research progress on photocatalytic, electrocatalytic and photoelectrocatalytic selective oxidation of 5-hydroxymethylfurfural","authors":"Yang An, Tao Lei, Weiyi Jiang and Huan Pang","doi":"10.1039/D4GC03597F","DOIUrl":"https://doi.org/10.1039/D4GC03597F","url":null,"abstract":"<p >Due to the increasing demand for fossil fuel resources in modern society, attention is turning towards alternative sources. This paper firstly introduces the importance of the oxidation reaction of 5-hydroxymethylfurfural (HMF) and its widespread application in the field of biomass conversion. However, precise control over the selective oxidation of biomass-derived platform chemicals remains challenging, necessitating in-depth investigation into the mechanism of this oxidation process. Subsequently, the mechanism of the HMF oxidation reaction is discussed in detail, including the design and performance optimization of both traditional and novel catalysts, aiming to provide theoretical guidance and technical support for efficient and selective HMF oxidation. In the field of photocatalysis, strategies such as the introduction of photoresponsive catalysts, surface modification, and synergistic catalysis have been employed to enhance reaction rates and selectivity. In electrocatalysis, efficient conversion of HMF has been achieved through the modulation of catalyst structure and active sites. Meanwhile, photoelectrocatalysis hybrid systems, as emerging technologies integrating the advantages of both photocatalysis and electrocatalysis, demonstrate promising application prospects, with an overview of their research in HMF oxidation provided herein. Furthermore, the paper discusses the challenges faced by current selective HMF oxidation, including catalyst stability, selectivity, and product distribution, and proposes future research directions and prospects, including the design of multifunctional catalysts, optimization of reaction conditions, and in-depth exploration of catalytic mechanisms, to provide important references for achieving efficient biomass conversion. In summary, this paper systematically summarizes the latest research progress in selective photocatalysis, electrocatalysis, and photoelectrocatalysis for HMF oxidation, and provides prospects for future development, aiming to offer references and insights for relevant research fields.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Monoliths enabling biocatalysis in flow chemistry","authors":"Aleksandra Lambarska, Katarzyna Szymańska and Ulf Hanefeld","doi":"10.1039/D4GC03535F","DOIUrl":"https://doi.org/10.1039/D4GC03535F","url":null,"abstract":"<p >This is a review on the feasibility of monolithic porous supports in biocatalysis carried out in a continuous flow system. It discusses factors affecting the efficiency and stability of enzyme immobilisation, kinetic parameters of enzyme processes carried out inside a monolith, biocatalysis in single and two-phase systems, and cascade reactions including cofactor regeneration. It also covers materials engineering (monolith types) and issues related to the flow of reactants through the monolith (chemical engineering). Emphasis is placed on the fact that the application of (bio)catalysis improves selectivity and atom economy, thus lowering the <em>E</em> factor. However, biocatalysts need to be employed in a reactor, which can aid further improvement towards green chemistry goals. The application of enzymes in flow chemistry has been shown to lead to higher space time yields (STYs) compared to batch reactions. In particular, with monolithic reactors a drastic decrease in volume and thus solvent can be achieved. By immobilising very high densities of enzymes directly on the monolith, reaction times dwindle, improving STYs. The small reaction volumes enable excellent heat transfer, helping to save energy. The underlying principles of monolithic flow reactors and their application in mono- and bi-phasic biocatalytic systems will be examined.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc03535f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Expression of concern: Preparation of polydopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles with a core/shell nanostructure as heterogeneous and recyclable nanocatalysts for the acetylation of alcohols, phenols, amines and thiols under solvent-free conditions","authors":"Hojat Veisi, Sepideh Taheri and Saba Hemmati","doi":"10.1039/D4GC90106A","DOIUrl":"https://doi.org/10.1039/D4GC90106A","url":null,"abstract":"<p >Expression of concern for ‘Preparation of polydopamine sulfamic acid-functionalized magnetic Fe<small>₃</small>O<small>₄</small> nanoparticles with a core/shell nanostructure as heterogeneous and recyclable nanocatalysts for the acetylation of alcohols, phenols, amines and thiols under solvent-free conditions’ by Hojat Veisi <em>et al.</em>, <em>Green Chem.</em>, 2016, <strong>18</strong>, 6337–6348, https://doi.org/10.1039/C6GC01975G.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc90106a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Scaling up clean production of biomass-derived organic acids as a step towards the realization of dual carbon goals: a review","authors":"Zulfiqar Ali, Jiliang Ma and Runcang Sun","doi":"10.1039/D4GC03829K","DOIUrl":"https://doi.org/10.1039/D4GC03829K","url":null,"abstract":"<p >The contemporary world faces issues related to energy, the environment, and food security. The use of carbon capture, storage, and utilization technologies can help reduce CO<small>₂</small> emissions from fossil fuels, which will result in major advancements toward dual carbon targets. In addition to promoting environmentally friendly manufacturing, chemical industries may replace fossil fuel-based raw materials with renewable biomass for the synthesis of organic acids and syngas. Although several studies are being conducted on co-valorization of CO<small>₂</small> and biomass feedstocks to produce organic acids and fine chemicals using biotechnology, thermocatalysis, electrocatalysis, and photocatalysis, there are still various obstacles in scaling up clean production, including (i) addressing environmental concerns, (ii) the intricate structure and chemical composition of biomass, (iii) conversion mechanisms and processes, (iv) designing catalyst materials with higher durability and recyclability, (v) greener solvent systems for catalysis and extraction, (vi) the deployment of modern technologies for characterization, (vii) training and guidelines for industrial operations, and (viii) governmental financing and policy. The sustainable manufacturing of biobased products from raw feedstocks produced from biomass has been made possible <em>via</em> technological breakthroughs in photo-/biorefineries, which are essential for the clean and environmentally friendly synthesis of organic acids. It is anticipated that clean production of organic acids from biomass will have a dominant market share, benefiting from both socioeconomic and environmental factors. With future technical developments, the valorization of feedstocks obtained from biomass together with CO<small>₂</small> for manufacturing fuels and fine chemicals will be more ecologically and economically feasible.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Straightforward solid-phase modification of TiO2 with propylphosphonic acid via manual grinding and shaker mixing: enhancing modification degree by thermal control while improving atom economy†","authors":"Kaimin Zhang, Jinxin Wang, Nick Gys, Elien Derveaux, Nahal Ghanemnia, Wouter Marchal, Peter Adriaensens and Vera Meynen","doi":"10.1039/D4GC03330B","DOIUrl":"https://doi.org/10.1039/D4GC03330B","url":null,"abstract":"<p >Grafting organophosphonic acids (PAs) on metal oxides has shown to be a flexible technology to tune the surface properties of metal oxides for various applications. The solvents applied in the commonly used synthesis method have associated impeding effect on tailoring the resulting modification degree. In this work, an alternative solid-phase manual grinding method is proposed that (i) is straightforward, (ii) can achieve controllable and higher modification degree, and (iii) excludes the use of solvent during the synthesis. Specifically, propylphosphonic acid (3PA) was grafted onto titania by manual grinding, and different modification degrees were obtained by varying the duration of the post-synthetic thermal treatment. Importantly, the solid-phase method can achieve a modification degree that is 25.0% higher than the maximal modification degree reached by the liquid-phase method, while its atom utilization efficiency is 4.8 times (toluene-based) or 7.5 times (water-based) that of the liquid-phase method.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc03330b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}