Green Chemistry最新文献

{"title":"Poly(carbonate acetal) vitrimers with enhanced thermal properties and closed-loop thermal recyclability derived from waste polycarbonate-derived polyaldehyde and pentaerythritol/erythritol/D-sorbitol","authors":"Yi-Chun Chen, Kamani Sudhir K. Reddy, Ru-Jong Jeng, Ching-Hsuan Lin","doi":"10.1039/d4gc02934h","DOIUrl":"https://doi.org/10.1039/d4gc02934h","url":null,"abstract":"We synthesized three poly(carbonate acetal) vitrimers (PCA-P, PCA-E, PCA-S) by condensing a waste polycarbonate-derived polyaldehyde (WPC-CHO) with pentaerythritol, erythritol, and <small>D</small>-sorbitol, using 0.5–4.0 mol% <em>p</em>-toluene sulfonic acid (<em>p</em>TSA) as a catalyst. Flexible PCA films emerged at <em>p</em>TSA concentrations ≥1 mol%, indicating a critical threshold of acid for effective condensation. The glass transition temperatures (<em>T</em><small>_g</small>) of the films remained consistent across <em>p</em>TSA concentrations but varied based on the multi-alcohol structure, with <em>T</em><small>_g</small> values of 178 °C for both PCA-P and PCA-S, and 142 °C for PCA-E, suggesting superior performance of pentaerythritol and <small>D</small>-sorbitol over erythritol as building blocks. Among these, the PCA-S series exhibited the best performance and utilized the least expensive starting materials, achieving the highest cost-performance index. The PCAs, featuring covalent adaptable polyacetal networks, facilitated thermal reprocessing through acetal metathesis. The second reprocessed PCA-P and PCA-S maintained similar thermal and mechanical properties to their original forms, demonstrating a closed-loop recycling. These polymers showed stability in THF/H<small>₂</small>O (4/1) with 0.1–1.0 M H<small>₂</small>SO<small>₄</small> at 25 °C, but can be degraded at 50 °C within 5 hours in both 0.5 M H<small>₂</small>SO<small>₄</small> and HCl THF/H<small>₂</small>O (4/1) solutions. NMR analysis of the degraded PCA-P confirmed the recovery of WPC-CHO and pentaerythritol. Furthermore, PCA-based carbon-fiber-reinforced plastics (CFRPs) were prepared, and the carbon fibers were successfully recovered after acid degradation without any loss to their structural or tensile integrity.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195732","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":"Enantioselective electrosynthesis of inherently chiral calix[4]arenes via a cobalt-catalyzed aryl C–H acyloxylation","authors":"Liming Zhang, Chen Yang, Xinhai Wang, Taixin Yang, Dandan Yang, Yingchao Dou, Jun-Long Niu","doi":"10.1039/d4gc02877e","DOIUrl":"https://doi.org/10.1039/d4gc02877e","url":null,"abstract":"Inherently chiral calixarenes are known to exhibit versatile functions due to their delicate three-dimensional macrocyclic frameworks. However, the catalytic asymmetric synthesis of these compounds remains largely unexplored and poses a significant challenge. Herein, we report an unprecedented enantioselective electrochemical synthesis of inherently chiral calix[4]arenes. Our approach is based on a 3d metal cobalt-catalyzed asymmetric C–H acyloxylation of the prochiral macrocyclic frameworks. The easily accessible and modifiable chiral salicyloxazoline (Salox) was used as the ligand to efficiently regulate the enantioselectivity. This protocol proceeded smoothly under electrochemically mild conditions and was compatible with a wide range of carboxylic acids, including aryl carboxylic acids and tertiary, secondary, primary aliphatic carboxylic acids, yielding a variety of acyloxylated calix[4]arenes with good yields (up to 94% yield) and excellent enantioselectivities (95–99% ee). The synthetic practicability of this method was demonstrated by the scale-up reaction and the divergent derivatizations of the inherently chiral macrocyclic products.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195751","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":"Environmentally friendly Miyaura Borylations allowing for green, 1-pot borylation/Suzuki–Miyaura couplings","authors":"Chandler B. Nelson, Scott J. L'Heureux, Madison J. Wong, Simone L. Kuhn, Erika Ghiglietti, Bruce H. Lipshutz","doi":"10.1039/d4gc03115f","DOIUrl":"https://doi.org/10.1039/d4gc03115f","url":null,"abstract":"Current routes to boronic acids and their corresponding esters to be used in subsequent Suzuki–Miyaura (SM) cross couplings impact the cost, waste, and safety concerns associated with generating these materials. A new method for installing the ethyl pinacol boronic ester, or B(Epin) derivative leads to stable borylated products under near-neat conditions using high concentrations of a green solvent and moderate reaction temperatures, catalyzed by relatively low palladium loadings. Alternatively, the newly fashioned Ar–B(Epin) can be generated <em>in situ</em> and used directly in the same pot for SM reactions leading to aromatic and heteroaromatic residues characteristic of the biaryl products being formed. An array of complex targets, including API-related products, can be generated <em>via</em> this green and environmentally responsible methodology.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195729","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":"Designing green chemicals by predicting vaporization properties using explainable graph attention networks","authors":"Yeonjoon Kim, Jaeyoung Cho, Hojin Jung, Lydia E. Meyer, Gina M. Fioroni, Christopher D. Stubbs, Keunhong Jeong, Robert L. McCormick, Peter C. St. John, Seonah Kim","doi":"10.1039/d4gc01994f","DOIUrl":"https://doi.org/10.1039/d4gc01994f","url":null,"abstract":"Computational predictions of vaporization properties aid the <em>de novo</em> design of green chemicals, including clean alternative fuels, working fluids for efficient thermal energy recovery, and polymers that are easily degradable and recyclable. Here, we developed chemically explainable graph attention networks to predict five physical properties pertinent to performance in utilizing renewable energy: heat of vaporization (HoV), critical temperature, flash point, boiling point, and liquid heat capacity. The predictive model for HoV was trained using ∼150 000 data points, considering their uncertainties and temperature dependence. Next, this model was expanded to the other properties through transfer learning to overcome the limitations due to fewer data points (700–7500). The chemical interpretability of the model was then investigated, demonstrating that the model explains molecular structural effects on vaporization properties. Finally, the developed predictive models were applied to design chemicals that have desirable properties as efficient and green working fluids, fuels, and polymers, enabling fast and accurate screening before experiments.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195728","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":"General electron–donor–acceptor complex mediated thioesterification reaction via site-selective C–H functionalization using aryl sulfonium Salts","authors":"Roshan I. Patel, Barakha Saxena, Anuj Sharma","doi":"10.1039/d4gc03768e","DOIUrl":"https://doi.org/10.1039/d4gc03768e","url":null,"abstract":"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.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-09-03","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":"Direct deoxygenative C–N coupling to construct indazole under visible light","authors":"Xinluo Song, Lingfeng Yin, Subin Hao, Yu Wang, Yanqi Chen, Cheng Ma, Ming-De Li, Li Dang","doi":"10.1039/d4gc02807d","DOIUrl":"https://doi.org/10.1039/d4gc02807d","url":null,"abstract":"The green synthesis of medicines with an indazole skeleton has gained significant attention in recent years. Sustainable and environmentally friendly approaches for the synthesis of this important class of heterocyclic compounds from azobenzenes are attractive but rare. In this work, a series of neat, fast, and efficient reactions are well developed as a notable methodology for the photo-organic synthesis of indazoles. Metal and hydrogen source-free direct deoxygenative cyclization of <em>o</em>-carbonyl azobenzene under visible light is achieved through a new mechanism with huge potential in reduction cyclization reactions. Most examples are shown to give the corresponding 2<em>H</em>-indazole products in excellent yields, demonstrating that the present reaction has a wide substrate scope and good functional group tolerance.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142264452","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":"Efficient and selective extraction of oleanolic acid from grape pomace with dimethyl carbonate","authors":"Francesco Errichiello, Raffaele Cucciniello, Michele Tomasini, Laura Falivene, Angelita Gambuti, Chiara Cassiano, Martino Forino","doi":"10.1039/d4gc03624g","DOIUrl":"https://doi.org/10.1039/d4gc03624g","url":null,"abstract":"Grape pomace is a major winery solid residue and several tons are annually produced worldwide. Since it is a valuable source of high value-added compounds, many strategies have been implemented for its valorization. The extraction of bioactive molecules with a broad range of applications is certainly the most investigated topics. In this context, oleanolic acid, a triterpenoid with a relevant biological activity, has been recently detected in grape pomace in remarkable quantities (0.45 mg per gram of fresh pomace). Herein, we report on a selective extraction of oleanolic acid from grape pomace by using dimethyl carbonate (DMC), a recommended green solvent as a better alternative to fossil-based solvents. Chemical–physical properties, Hildebrand's solubility and Kamlet–Abboud–Taft parameters have been considered to select a greener alternative to fossil-based solvents and theoretical calculations have been performed to determine the interaction between DMC and the oleanolic acid. The obtained grape pomace extracts were characterized by means of NMR and LC-MS. DMC allows the recovery of oleanolic acid from grape pomace, due to its weak polarity and poor ability to form H-bonds, with a molar selectivity of 61%, thus promoting the adoption of alternative green and sustainable technologies for biomass residue valorization. Also, DMC was recycled and reused in three consecutive extractions and no significant losses in terms of oleanolic acid extraction yield were detected.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195731","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":"Catalytic pyrolysis mechanism of lignin moieties driven by aldehyde, hydroxyl, methoxy, and allyl functionalization: the role of reactive quinone methide and ketene intermediates†","authors":"Zeyou Pan, Xiangkun Wu, Andras Bodi, Jeroen A. van Bokhoven and Patrick Hemberger","doi":"10.1039/D4GC03143A","DOIUrl":"10.1039/D4GC03143A","url":null,"abstract":"<p >The catalytic pyrolysis of guaiacol-based lignin monomers, vanillin, syringol, and eugenol over commercial HZSM-5 has been investigated using <em>operando</em> Photoelectron Photoion Coincidence (PEPICO) spectroscopy to unveil the reaction mechanism by detecting reactive intermediates, such as quinone methides and ketenes, and products. <em>Vanillin</em> shares the decomposition mechanism with guaiacol due to prompt and efficient decarbonylation, which allows us to control this reaction leading to a phenol selectivity increase by switching to a faujasite catalyst and decreasing the Si/Al ratio. <em>Syringol</em> first demethylates to 3-methoxycatechol, which mainly dehydroxylates to <em>o</em>- and <em>m</em>-guaiacol. Ketene formation channels over HZSM-5 are less important here than for guaiacol or vanillin, but product distribution remains similar. C<small>₃</small> addition to guaiacol yields <em>eugenol</em>, which shows a more complex product distribution upon catalytic pyrolysis. By analogies to monomers with simplified functionalization, namely allylbenzene, 4-allylcatechol, and 4-methylcatechol, the eugenol chemistry could be fully resolved. Previously postulated reactive semi-quinone intermediates are detected spectroscopically, and their involvement opens alternative pathways to condensation and phenol formation. Allyl groups, produced by dehydroxylation of the β-O-4 bond, may not only decompose <em>via</em> C1/C2/C3 loss, but also cyclize to indene and its derivatives over HZSM-5. This comparably high reactivity leads to an unselective branching of the chemistry and to a complex product distribution, which is difficult to control. Indenes and naphthalenes are also prototypical coke precursors efficiently deactivating the catalyst. We rely on these mechanistic insights to discuss strategies to fine-tune process conditions to increase the selectivities of desired products by enhancing either vanillin and guaiacol or supressing eugenol yields from native lignin.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11363027/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102313","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":"Acid-catalyzed regioselective remote heteroarylation of alkenes via CC bond migration","authors":"Shengxiang Qin, Yaqi Zhang, Long Jiang, Man Kin Tse, Albert S. C. Chan, Liqin Qiu","doi":"10.1039/d4gc03356f","DOIUrl":"https://doi.org/10.1039/d4gc03356f","url":null,"abstract":"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)<small>₂</small> and trace H<small>₂</small>O catalyzed the alkene migration. Then, heteroarylation was conducted by Friedel–Crafts type alkylation.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-08-30","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":"Exploiting natural complexity for substrate controlled regioselectivity and stereoselectivity in tantalum catalysed hydroaminoalkylation†","authors":"Cameron H. M. Zheng, Ben E. Nadeau, Heather L. Trajano and Laurel L. Schafer","doi":"10.1039/D4GC01614A","DOIUrl":"10.1039/D4GC01614A","url":null,"abstract":"<p >Naturally occurring and structurally diverse alkene-containing substrates, terpenes, provided a platform for establishing chemo-, regio-, and diastereoselective reactivity in tantalum catalysed hydroaminoalkylation. Naturally derived 1,3-butadienes revealed the unique regio- and diastereoselective (<em>Z</em>)-1,4-addition products accessible from isoprene and β-myrcene by hydroaminoalkylation. Selective terpene functionalisation, within an industrially produced turpentine mixture, demonstrates functionalisation specificity of β-pinene and limonene. Lastly, sesquiterpene functionalisation using β-caryophyllene and humulene provide rare examples of trisubstituted alkene reactivity in hydroaminoalkylation, by leveraging strain-release and stereoelectronic effects to control chemoselectivity. As a result of these reactivity studies using natural substrates, new tools for understanding alkene electronic, strain, and stereoelectronic effects on chemo- and diastereoselectivity outcomes have revealed new mechanistic insights into hydroaminoalkylation.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195733","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}