Yong Yuan, Hangfei Jiang, Ya-Nan Zhang, Yuyan Tao, Xincong Liu and Congde Huo
An electroreductive deoxygenative carboxylation of alkyl oxalates with CO2 is demonstrated for the first time, which offers a general and scalable method for obtaining various carboxylic acids. This electrochemical method features a broad substrate scope and mild reaction conditions; various secondary benzyl alcohols and non-benzylic alcohols, primary benzyl alcohols and non-benzylic alcohols, and tertiary benzyl alcohols and non-benzylic alcohols can be converted into the corresponding carboxylic acids in good to excellent yields. Importantly, this electroreductive deoxygenative carboxylation reaction also offers a mild and straightforward route to access drug molecules, such as ibuprofen, (±) naproxen, fenoprofen, hexaprofen, and biprofen.
{"title":"Electroreductive deoxygenative carboxylation of alkyl oxalates with CO2†","authors":"Yong Yuan, Hangfei Jiang, Ya-Nan Zhang, Yuyan Tao, Xincong Liu and Congde Huo","doi":"10.1039/D4GC03452J","DOIUrl":"https://doi.org/10.1039/D4GC03452J","url":null,"abstract":"<p >An electroreductive deoxygenative carboxylation of alkyl oxalates with CO<small><sub>2</sub></small> is demonstrated for the first time, which offers a general and scalable method for obtaining various carboxylic acids. This electrochemical method features a broad substrate scope and mild reaction conditions; various secondary benzyl alcohols and non-benzylic alcohols, primary benzyl alcohols and non-benzylic alcohols, and tertiary benzyl alcohols and non-benzylic alcohols can be converted into the corresponding carboxylic acids in good to excellent yields. Importantly, this electroreductive deoxygenative carboxylation reaction also offers a mild and straightforward route to access drug molecules, such as ibuprofen, (±) naproxen, fenoprofen, hexaprofen, and biprofen.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 10811-10817"},"PeriodicalIF":9.3,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524317","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}
Dingyi Yang, Qi Zeng, Kaiwen Tan, Haoyue Hou, Xingyuan Fang, Chenlong Guo, Hao Yuan and Tao Meng
Light-responsive Pickering interfacial biocatalysis (LPIB) is desirable because of its convenient catalyst recovery, product separation and clean external stimuli trigger. However, the recyclability of LPIB is still limited due to its enzyme inactivation. Herein, lipase-entrapped colloidosomes as particulate emulsifiers and biocatalysts were fabricated using the one-step co-assembly of lipases and TiO2 nanoparticles (with light-responsive wettability). The obtained LPIB exhibited a 4.31-fold enhancement of enzyme activity compared with the traditional biphasic system. Impressively, the LPIB maintained nearly 90% of its initial enzyme activity even after 20 cycles, which is the highest among the currently reported LPIBs. It is attributed that the TiO2 nanoparticle layer on the colloidosome surface reflects UV light, thus protecting the enzyme from photodegradation. This green platform can be widely applied to construct recyclable and efficient biphasic biocatalytic systems.
{"title":"Lipase-entrapped colloidosomes with light-responsive wettability for efficient and recyclable Pickering interfacial biocatalysis†","authors":"Dingyi Yang, Qi Zeng, Kaiwen Tan, Haoyue Hou, Xingyuan Fang, Chenlong Guo, Hao Yuan and Tao Meng","doi":"10.1039/D4GC03982C","DOIUrl":"https://doi.org/10.1039/D4GC03982C","url":null,"abstract":"<p >Light-responsive Pickering interfacial biocatalysis (LPIB) is desirable because of its convenient catalyst recovery, product separation and clean external stimuli trigger. However, the recyclability of LPIB is still limited due to its enzyme inactivation. Herein, lipase-entrapped colloidosomes as particulate emulsifiers and biocatalysts were fabricated using the one-step co-assembly of lipases and TiO<small><sub>2</sub></small> nanoparticles (with light-responsive wettability). The obtained LPIB exhibited a 4.31-fold enhancement of enzyme activity compared with the traditional biphasic system. Impressively, the LPIB maintained nearly 90% of its initial enzyme activity even after 20 cycles, which is the highest among the currently reported LPIBs. It is attributed that the TiO<small><sub>2</sub></small> nanoparticle layer on the colloidosome surface reflects UV light, thus protecting the enzyme from photodegradation. This green platform can be widely applied to construct recyclable and efficient biphasic biocatalytic systems.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":" 21","pages":" 10824-10828"},"PeriodicalIF":9.3,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142524319","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}
Yi-Chun Chen , Kamani Sudhir K. Reddy , Ru-Jong Jeng , Ching-Hsuan Lin
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 d-sorbitol, using 0.5–4.0 mol% p-toluene sulfonic acid (pTSA) as a catalyst. Flexible PCA films emerged at pTSA concentrations ≥1 mol%, indicating a critical threshold of acid for effective condensation. The glass transition temperatures (Tg) of the films remained consistent across pTSA concentrations but varied based on the multi-alcohol structure, with Tg values of 178 °C for both PCA-P and PCA-S, and 142 °C for PCA-E, suggesting superior performance of pentaerythritol and d-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/H2O (4/1) with 0.1–1.0 M H2SO4 at 25 °C, but can be degraded at 50 °C within 5 hours in both 0.5 M H2SO4 and HCl THF/H2O (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.
{"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":"10.1039/d4gc02934h","url":null,"abstract":"<div><div>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 <span>d</span>-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><sub>g</sub>) of the films remained consistent across <em>p</em>TSA concentrations but varied based on the multi-alcohol structure, with <em>T</em><sub>g</sub> values of 178 °C for both PCA-P and PCA-S, and 142 °C for PCA-E, suggesting superior performance of pentaerythritol and <span>d</span>-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<sub>2</sub>O (4/1) with 0.1–1.0 M H<sub>2</sub>SO<sub>4</sub> at 25 °C, but can be degraded at 50 °C within 5 hours in both 0.5 M H<sub>2</sub>SO<sub>4</sub> and HCl THF/H<sub>2</sub>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.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10275-10289"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","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}
Liming Zhang , Chen Yang , Xinhai Wang , Taixin Yang , Dandan Yang , Yingchao Dou , Jun-Long Niu
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.
众所周知，手性烛石因其精致的三维大环框架而具有多种功能。然而，这些化合物的催化不对称合成在很大程度上仍未得到探索，并构成了一项重大挑战。在此，我们报告了一种前所未有的手性钙[4]炔的对映选择性电化学合成方法。我们的方法基于 3d 金属钴催化的原手性大环框架的不对称 C-H 乙酰氧基化。我们使用了易于获得和修饰的手性水杨酰噁唑啉（Salox）作为配体，以有效调节对映体选择性。该方法在电化学温和的条件下顺利进行，并与多种羧酸兼容，包括芳基羧酸和三级、二级、一级脂肪族羧酸，得到了多种酰氧基化的钙[4]炔，收率高（达 94%），对映体选择性好（95-99% ee）。该方法的合成实用性通过放大反应和固有手性大环产物的衍生化得到了证明。
{"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":"10.1039/d4gc02877e","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10232-10239"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","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}
Nan Wu , Mingdong Yao , Wenhai Xiao , Ying Wang , Ying-Jin Yuan
Lysergic acid (LA) is the basic precursor for the biosynthesis of various ergot alkaloids of pharmaceutical importance. The heterologous biosynthesis of LA in microbes is a promising method to reduce industrial dependence on highly costly and toxic crop-pathogenic ergot fungi. However, the biosynthetic efficiency of LA remains unsatisfactory because of the lack of effective pathways and low heterologous production performance. In this work, a microbial host, specifically a Saccharomyces cerevisiae strain, was constructed by applying a metabolic engineering strategy for efficient LA production. The SCH9 knockout was identified as a key factor for enhancing LA yield. Transcriptional analysis revealed that SCH9 deletion significantly enhanced peroxisomal metabolism and cellular translation. Accordingly, tailored approaches were designed to optimize the activities of two rate-limiting enzymes, EasC and CloA, in SCH9 deletion strains. The relocation of EasC to peroxisomes combined with PEX34 overexpression clearly increased the catalytic activity of these enzymes, increasing LA production by 2.31-fold. Moreover, spatial reorientation of the cytochrome P450 CloA and its reductase on the endoplasmic reticulum was performed, which improved electron transfer efficiency, resulting in a 36.8% improvement in LA production. These engineering strategies finally led to a 17.4-fold increase in the LA titre. The final engineered strain produced 509.8 mg L−1 LA under 50 L fed-batch fermentation, yielding the highest reported titre for heterologous hosts. These findings demonstrated a green alternative to the current ergot-based routes, offering a versatile platform for the sustainable, large-scale fermentation of pharmaceutical ergot alkaloids.
麦角酸（LA）是生物合成各种具有重要药用价值的麦角生物碱的基本前体。在微生物中异源生物合成 LA 是一种很有前途的方法，可以减少工业对高成本、高毒性的作物致病麦角菌的依赖。然而，由于缺乏有效途径和异源生产性能低下，LA 的生物合成效率仍不令人满意。在这项工作中，通过应用高效生产 LA 的代谢工程策略，构建了微生物宿主，特别是酿酒酵母菌株。SCH9基因敲除被认为是提高LA产量的关键因素。转录分析表明，SCH9 基因缺失可显著增强过氧物酶体代谢和细胞翻译。因此，设计了量身定制的方法来优化 SCH9 基因缺失菌株中两种限速酶 EasC 和 CloA 的活性。将 EasC 移至过氧化物酶体并结合 PEX34 的过表达，明显提高了这两种酶的催化活性，使 LA 的产量增加了 2.31 倍。此外，还对内质网上的细胞色素 P450 CloA 及其还原酶进行了空间定向，提高了电子传递效率，从而使 LA 产量提高了 36.8%。这些工程策略最终使 LA 滴度提高了 17.4 倍。最终的工程菌株在 50 升饲料批量发酵条件下产生了 509.8 mg L-1 的 LA，是目前报道的异源宿主最高滴度。这些研究结果表明，目前基于麦角的发酵路线是一种绿色替代方案，为可持续、大规模发酵药用麦角生物碱提供了一个多功能平台。
{"title":"Highly efficient synthesis of lysergic acid using engineered budding yeast†","authors":"Nan Wu , Mingdong Yao , Wenhai Xiao , Ying Wang , Ying-Jin Yuan","doi":"10.1039/d4gc03756a","DOIUrl":"10.1039/d4gc03756a","url":null,"abstract":"<div><div>Lysergic acid (LA) is the basic precursor for the biosynthesis of various ergot alkaloids of pharmaceutical importance. The heterologous biosynthesis of LA in microbes is a promising method to reduce industrial dependence on highly costly and toxic crop-pathogenic ergot fungi. However, the biosynthetic efficiency of LA remains unsatisfactory because of the lack of effective pathways and low heterologous production performance. In this work, a microbial host, specifically a <em>Saccharomyces cerevisiae</em> strain, was constructed by applying a metabolic engineering strategy for efficient LA production. The <em>SCH9</em> knockout was identified as a key factor for enhancing LA yield. Transcriptional analysis revealed that <em>SCH9</em> deletion significantly enhanced peroxisomal metabolism and cellular translation. Accordingly, tailored approaches were designed to optimize the activities of two rate-limiting enzymes, EasC and CloA, in <em>SCH9</em> deletion strains. The relocation of EasC to peroxisomes combined with <em>PEX34</em> overexpression clearly increased the catalytic activity of these enzymes, increasing LA production by 2.31-fold. Moreover, spatial reorientation of the cytochrome P450 CloA and its reductase on the endoplasmic reticulum was performed, which improved electron transfer efficiency, resulting in a 36.8% improvement in LA production. These engineering strategies finally led to a 17.4-fold increase in the LA titre. The final engineered strain produced 509.8 mg L<sup>−1</sup> LA under 50 L fed-batch fermentation, yielding the highest reported titre for heterologous hosts. These findings demonstrated a green alternative to the current ergot-based routes, offering a versatile platform for the sustainable, large-scale fermentation of pharmaceutical ergot alkaloids.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10330-10343"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142264447","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}
The utilization of mild and environment-friendly reaction conditions for the photocatalytic oxidation of sulfides to highly valuable sulfoxides represents a sustainable approach that is highly desirable yet quite challenging. Herein, we present a novel approach to enhance the photocatalytic oxidation of sulfides in water by molecular structural engineering of donor–acceptor (D–A) based polymeric networks. By incorporating electron-deficient heptazine or triazine units as acceptors and electron-rich 2,5-diamino fluorene as donors, a synergistic effect is achieved, promoting efficient charge separation upon light absorption. The two polymeric networks namely HEP-FL and TZ-FL efficiently carried out selective oxidation of sulfides to sulfoxide with 100% conversion within 1.3 h and 3.5 h, respectively under blue light irradiation. Through advanced spectroscopic and electrochemical measurements, the correlation between molecular structures and optoelectronic properties is elucidated, unveiling tunable band structures and exciton binding energies. Notably, the heptazine-containing polymeric network (HEP-FL) exhibited superior charge separation efficiency and enhanced catalytic activity, attributed to improved electron delocalization and reduced exciton binding energy. Additionally, we have performed green metrics calculations for the synthesis of sulfoxide using HEP-FL as a photocatalyst to prove the sustainability of the reaction system. These findings underscore the significant prospects of donor–acceptor-based polymeric networks as highly effective photocatalysts for selective oxidation reactions, highlighting their potential to advance environmentally conscious practices in organic synthesis and industrial applications.
{"title":"Molecular structural engineering of donor–acceptor-based porous organic polymers for sulfide photooxidation in water: a sustainable approach†","authors":"Neha Saini , Kirti Dhingra , Amit Kumar , Kamalakannan Kailasam","doi":"10.1039/d4gc03255a","DOIUrl":"10.1039/d4gc03255a","url":null,"abstract":"<div><div>The utilization of mild and environment-friendly reaction conditions for the photocatalytic oxidation of sulfides to highly valuable sulfoxides represents a sustainable approach that is highly desirable yet quite challenging. Herein, we present a novel approach to enhance the photocatalytic oxidation of sulfides in water by molecular structural engineering of donor–acceptor (D–A) based polymeric networks. By incorporating electron-deficient heptazine or triazine units as acceptors and electron-rich 2,5-diamino fluorene as donors, a synergistic effect is achieved, promoting efficient charge separation upon light absorption. The two polymeric networks namely HEP-FL and TZ-FL efficiently carried out selective oxidation of sulfides to sulfoxide with 100% conversion within 1.3 h and 3.5 h, respectively under blue light irradiation. Through advanced spectroscopic and electrochemical measurements, the correlation between molecular structures and optoelectronic properties is elucidated, unveiling tunable band structures and exciton binding energies. Notably, the heptazine-containing polymeric network (HEP-FL) exhibited superior charge separation efficiency and enhanced catalytic activity, attributed to improved electron delocalization and reduced exciton binding energy. Additionally, we have performed green metrics calculations for the synthesis of sulfoxide using HEP-FL as a photocatalyst to prove the sustainability of the reaction system. These findings underscore the significant prospects of donor–acceptor-based polymeric networks as highly effective photocatalysts for selective oxidation reactions, highlighting their potential to advance environmentally conscious practices in organic synthesis and industrial applications.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10314-10323"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142269872","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}
To address the problem of non-renewable resources and energy shortages, converting biomass, the only renewable carbon resource on Earth, into various fine chemicals holds significant value. Furfural stands out as one of the most promising platform compounds derived from lignocellulosic biomass. Due to its highly functional molecular structure, furfural can be selectively converted into various fuels and high-value compounds. This review discusses recent developments in furfural production and its conversion into related chemicals, such as furfuryl alcohol, γ-valerolactone, pentanediols, and nitrogen-containing compounds. It provides an in-depth understanding of the catalysts, systems, and mechanisms used in the selective transformation of furfural. The review also explores primary pathways and catalytic mechanisms, with a focus on advances in heterogeneous catalytic systems. Furthermore, it outlines future research directions and offers insights into potential applications in this field. This review presents several research trends, aiming to provide innovative ideas for further exploration of furfural downstream products in a greener, more efficient, and cost-effective manner.
{"title":"Recent catalytic innovations in furfural transformation","authors":"","doi":"10.1039/d4gc01983k","DOIUrl":"10.1039/d4gc01983k","url":null,"abstract":"<div><div>To address the problem of non-renewable resources and energy shortages, converting biomass, the only renewable carbon resource on Earth, into various fine chemicals holds significant value. Furfural stands out as one of the most promising platform compounds derived from lignocellulosic biomass. Due to its highly functional molecular structure, furfural can be selectively converted into various fuels and high-value compounds. This review discusses recent developments in furfural production and its conversion into related chemicals, such as furfuryl alcohol, γ-valerolactone, pentanediols, and nitrogen-containing compounds. It provides an in-depth understanding of the catalysts, systems, and mechanisms used in the selective transformation of furfural. The review also explores primary pathways and catalytic mechanisms, with a focus on advances in heterogeneous catalytic systems. Furthermore, it outlines future research directions and offers insights into potential applications in this field. This review presents several research trends, aiming to provide innovative ideas for further exploration of furfural downstream products in a greener, more efficient, and cost-effective manner.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 9957-9992"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141146080","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}
Chandler B. Nelson , Scott J. L'Heureux , Madison J. Wong , Simone L. Kuhn , Erika Ghiglietti , Bruce H. Lipshutz
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 in situ 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 via this green and environmentally responsible methodology.
目前用于后续铃木-宫浦（SM）交叉偶联反应的硼酸及其相应酯类的制备路线会影响到与生成这些材料相关的成本、废物和安全问题。一种安装频哪醇乙硼酸酯或 B(Epin)衍生物的新方法，在相对较低的钯载量催化下，使用高浓度的绿色溶剂和适中的反应温度，在近乎无水的条件下生成稳定的硼酰化产物。另外，还可以在原位生成新的 Ar-B（表嘌呤），并直接在同一锅中用于 SM 反应，从而产生具有双芳基产物特征的芳香族和杂芳香族残留物。通过这种绿色环保的方法，可以生成一系列复杂的目标物，包括原料药相关产品。
{"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":"10.1039/d4gc03115f","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10115-10122"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","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}
Amrutham Vasu , Mameda Naresh , Gajula Krishna Sai , Boosa Murali , Dasu Suchitha , Avusali Sai Teja , Nama Narender
The synthesis of carbon–heteroatom bonds, a crucial element in organic chemistry, often requires obstacles in direct amine integration with olefins. This study introduces a sustainable approach for producing nitrogen-bearing molecules through the Markovnikov hydroamination of vinylarenes with carboxamides, employing Hβ zeolite as an effective heterogeneous catalyst in a solvent-free environment. We explored the method's adaptability over various substrates, achieving consistently high yields and regioselectivity in the resultant products. The procedure's scalability to gram-level production and the catalyst's sustainable reuse for multiple cycles (up to five) underscores its viability for industrial application, indicating a significant increase in organic synthesis activity.
{"title":"Solvent-free Markovnikov hydroamination of vinylarenes with carboxamides: a heterogeneous catalytic approach using Hβ zeolite†","authors":"Amrutham Vasu , Mameda Naresh , Gajula Krishna Sai , Boosa Murali , Dasu Suchitha , Avusali Sai Teja , Nama Narender","doi":"10.1039/d4gc04264f","DOIUrl":"10.1039/d4gc04264f","url":null,"abstract":"<div><div>The synthesis of carbon–heteroatom bonds, a crucial element in organic chemistry, often requires obstacles in direct amine integration with olefins. This study introduces a sustainable approach for producing nitrogen-bearing molecules through the Markovnikov hydroamination of vinylarenes with carboxamides, employing Hβ zeolite as an effective heterogeneous catalyst in a solvent-free environment. We explored the method's adaptability over various substrates, achieving consistently high yields and regioselectivity in the resultant products. The procedure's scalability to gram-level production and the catalyst's sustainable reuse for multiple cycles (up to five) underscores its viability for industrial application, indicating a significant increase in organic synthesis activity.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10064-10069"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329365","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}
Leonardo M. de Souza Mesquita , Leticia S. Contieri , Francisca A. e Silva , Rafael Henrique Bagini , Felipe S. Bragagnolo , Monique M. Strieder , Filipe H. B. Sosa , Nicolas Schaeffer , Mara G. Freire , Sónia P. M. Ventura , João A. P. Coutinho , Maurício A. Rostagno
We propose an innovative approach to address the pressing need for efficient and transparent evaluation techniques to assess extraction processes’ sustainability. In response to society's growing demand for natural products and the consequent surge in biomass exploration, a critical imperative arises to ensure that these processes are genuinely environmentally friendly. Extracting natural compounds has traditionally been regarded as a benign activity rooted in ancient practices. However, contemporary extraction methods can also significantly harm the environment if not carefully managed. Recognizing this, we developed a novel metric, Path2Green, tailored specifically and rooted in 12 new principles of a green extraction process. Path2Green seeks to provide a comprehensive framework beyond conventional metrics, offering a nuanced understanding of the environmental impact of extraction activities from biomass collection/production until the end of the process. By integrating factors such as resource depletion, energy consumption, waste generation, and biodiversity preservation, Path2Green aims to offer a holistic assessment of sustainability of an extraction approach. The significance of Path2Green lies in its ability to distill complex environmental data into a simple, accessible metric. This facilitates informed decision-making for stakeholders across industries, enabling them to prioritize greener extraction practices. Moreover, by setting clear benchmarks and standards, Path2Green incentivizes innovation and drives continuous improvement in sustainability efforts, being a new user-friendly methodology.
{"title":"Path2Green: introducing 12 green extraction principles and a novel metric for assessing sustainability in biomass valorization†","authors":"Leonardo M. de Souza Mesquita , Leticia S. Contieri , Francisca A. e Silva , Rafael Henrique Bagini , Felipe S. Bragagnolo , Monique M. Strieder , Filipe H. B. Sosa , Nicolas Schaeffer , Mara G. Freire , Sónia P. M. Ventura , João A. P. Coutinho , Maurício A. Rostagno","doi":"10.1039/d4gc02512a","DOIUrl":"10.1039/d4gc02512a","url":null,"abstract":"<div><div>We propose an innovative approach to address the pressing need for efficient and transparent evaluation techniques to assess extraction processes’ sustainability. In response to society's growing demand for natural products and the consequent surge in biomass exploration, a critical imperative arises to ensure that these processes are genuinely environmentally friendly. Extracting natural compounds has traditionally been regarded as a benign activity rooted in ancient practices. However, contemporary extraction methods can also significantly harm the environment if not carefully managed. Recognizing this, we developed a novel metric, <em>Path2Green</em>, tailored specifically and rooted in 12 new principles of a green extraction process. <em>Path2Green</em> seeks to provide a comprehensive framework beyond conventional metrics, offering a nuanced understanding of the environmental impact of extraction activities from biomass collection/production until the end of the process. By integrating factors such as resource depletion, energy consumption, waste generation, and biodiversity preservation, <em>Path2Green</em> aims to offer a holistic assessment of sustainability of an extraction approach. The significance of <em>Path2Green</em> lies in its ability to distill complex environmental data into a simple, accessible metric. This facilitates informed decision-making for stakeholders across industries, enabling them to prioritize greener extraction practices. Moreover, by setting clear benchmarks and standards, <em>Path2Green</em> incentivizes innovation and drives continuous improvement in sustainability efforts, being a new user-friendly methodology.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"26 19","pages":"Pages 10087-10106"},"PeriodicalIF":9.3,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc02512a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141946924","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}
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