Stefan S. Warthegau, Ana Jakob, Mads S. Christensen, Amalie Vestentoft, Miha Grilc, Blaž Likozar, Sebastian Meier
{"title":"用乙酰丙酮转化丰富的醛:揭示路易斯酸性盐在水中形成官能化呋喃的机理并改善对其的控制","authors":"Stefan S. Warthegau, Ana Jakob, Mads S. Christensen, Amalie Vestentoft, Miha Grilc, Blaž Likozar, Sebastian Meier","doi":"10.1021/acssuschemeng.4c05695","DOIUrl":null,"url":null,"abstract":"The exploration and exploitation of reactions extending abundant carbohydrates by multiple-bond-forming reactions have recently experienced a renaissance. Such reactions can form drug-like structural motifs from renewable substrates in water at mild temperatures. A combined reaction tracking and kinetic modeling approach was conducted here for the conversion of glucose and other simple carbohydrates with acetylacetone to densely functionalized furans in the Lewis-acid-catalyzed Garcia Gonzalezreaction in water. Real-time <sup>13</sup>C NMR data was used to identify major intermediates toward furan products, and kinetic modeling supports the deduced pathway and reveals its energetics. Albeit the main dihydrofuran intermediate is bicyclic, with the C4 oxygen of glucose attached to the dihydrofuran ring, the use of C4-functionalized carbohydrate (maltose) shows that this intermediate is not the only on-pathway intermediate toward functionalized furans. The use of nearly solvent-free eutectic mixtures favors the intermolecular initial steps and renders the conversion of glucose and acetylacetone largely complete within 4 h at 323 K, even in the presence of only 0.01 equiv Zr(IV). As the conversion proceeds in an initial bimolecular and subsequent unimolecular reaction, sufficiently high substrate concentrations favor the initial bimolecular reaction to polyhydroxyalkyl furan, which equilibrates with C-glycosyl furan. The use of various Lewis acid salt catalysts indicates that the conversion of glucose and acetylacetone is not uniquely favored by Zr(IV) catalysis. For instance, similarly efficient enolization of acetylacetone and reaction are achieved using Hf(IV) catalysis in water. Alternative media were correctly predicted to catalyze the reaction at milder temperatures along the same pathway, including a concentrated solution of ZnCl<sub>2</sub> in water that had previously been described as a nontoxic and recyclable homogeneous reaction medium for converting polysaccharides into dehydrated chemicals.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":7.1000,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Conversion of Abundant Aldoses with Acetylacetone: Unveiling the Mechanism and Improving Control in the Formation of Functionalized Furans Using Lewis Acidic Salts in Water\",\"authors\":\"Stefan S. Warthegau, Ana Jakob, Mads S. Christensen, Amalie Vestentoft, Miha Grilc, Blaž Likozar, Sebastian Meier\",\"doi\":\"10.1021/acssuschemeng.4c05695\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The exploration and exploitation of reactions extending abundant carbohydrates by multiple-bond-forming reactions have recently experienced a renaissance. Such reactions can form drug-like structural motifs from renewable substrates in water at mild temperatures. A combined reaction tracking and kinetic modeling approach was conducted here for the conversion of glucose and other simple carbohydrates with acetylacetone to densely functionalized furans in the Lewis-acid-catalyzed Garcia Gonzalezreaction in water. Real-time <sup>13</sup>C NMR data was used to identify major intermediates toward furan products, and kinetic modeling supports the deduced pathway and reveals its energetics. Albeit the main dihydrofuran intermediate is bicyclic, with the C4 oxygen of glucose attached to the dihydrofuran ring, the use of C4-functionalized carbohydrate (maltose) shows that this intermediate is not the only on-pathway intermediate toward functionalized furans. The use of nearly solvent-free eutectic mixtures favors the intermolecular initial steps and renders the conversion of glucose and acetylacetone largely complete within 4 h at 323 K, even in the presence of only 0.01 equiv Zr(IV). As the conversion proceeds in an initial bimolecular and subsequent unimolecular reaction, sufficiently high substrate concentrations favor the initial bimolecular reaction to polyhydroxyalkyl furan, which equilibrates with C-glycosyl furan. The use of various Lewis acid salt catalysts indicates that the conversion of glucose and acetylacetone is not uniquely favored by Zr(IV) catalysis. For instance, similarly efficient enolization of acetylacetone and reaction are achieved using Hf(IV) catalysis in water. Alternative media were correctly predicted to catalyze the reaction at milder temperatures along the same pathway, including a concentrated solution of ZnCl<sub>2</sub> in water that had previously been described as a nontoxic and recyclable homogeneous reaction medium for converting polysaccharides into dehydrated chemicals.\",\"PeriodicalId\":25,\"journal\":{\"name\":\"ACS Sustainable Chemistry & Engineering\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.1000,\"publicationDate\":\"2024-10-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Sustainable Chemistry & Engineering\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acssuschemeng.4c05695\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Sustainable Chemistry & Engineering","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acssuschemeng.4c05695","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Conversion of Abundant Aldoses with Acetylacetone: Unveiling the Mechanism and Improving Control in the Formation of Functionalized Furans Using Lewis Acidic Salts in Water
The exploration and exploitation of reactions extending abundant carbohydrates by multiple-bond-forming reactions have recently experienced a renaissance. Such reactions can form drug-like structural motifs from renewable substrates in water at mild temperatures. A combined reaction tracking and kinetic modeling approach was conducted here for the conversion of glucose and other simple carbohydrates with acetylacetone to densely functionalized furans in the Lewis-acid-catalyzed Garcia Gonzalezreaction in water. Real-time 13C NMR data was used to identify major intermediates toward furan products, and kinetic modeling supports the deduced pathway and reveals its energetics. Albeit the main dihydrofuran intermediate is bicyclic, with the C4 oxygen of glucose attached to the dihydrofuran ring, the use of C4-functionalized carbohydrate (maltose) shows that this intermediate is not the only on-pathway intermediate toward functionalized furans. The use of nearly solvent-free eutectic mixtures favors the intermolecular initial steps and renders the conversion of glucose and acetylacetone largely complete within 4 h at 323 K, even in the presence of only 0.01 equiv Zr(IV). As the conversion proceeds in an initial bimolecular and subsequent unimolecular reaction, sufficiently high substrate concentrations favor the initial bimolecular reaction to polyhydroxyalkyl furan, which equilibrates with C-glycosyl furan. The use of various Lewis acid salt catalysts indicates that the conversion of glucose and acetylacetone is not uniquely favored by Zr(IV) catalysis. For instance, similarly efficient enolization of acetylacetone and reaction are achieved using Hf(IV) catalysis in water. Alternative media were correctly predicted to catalyze the reaction at milder temperatures along the same pathway, including a concentrated solution of ZnCl2 in water that had previously been described as a nontoxic and recyclable homogeneous reaction medium for converting polysaccharides into dehydrated chemicals.
期刊介绍:
ACS Sustainable Chemistry & Engineering is a prestigious weekly peer-reviewed scientific journal published by the American Chemical Society. Dedicated to advancing the principles of green chemistry and green engineering, it covers a wide array of research topics including green chemistry, green engineering, biomass, alternative energy, and life cycle assessment.
The journal welcomes submissions in various formats, including Letters, Articles, Features, and Perspectives (Reviews), that address the challenges of sustainability in the chemical enterprise and contribute to the advancement of sustainable practices. Join us in shaping the future of sustainable chemistry and engineering.