Pub Date : 2025-02-27DOI: 10.1016/j.tgchem.2025.100071
Huiying Xu, Huidan Luo, Yi Wang, Hui Gao
1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a solvent with unique properties. In recent years, it has received widespread attention due to its ability to stabilize ionic species, transfer protons, and participate in a range of intermolecular interactions, demonstrating excellent benefits in facilitating a variety of challenging chemical reactions. In this review, after a brief introduction to the physical and chemical properties of HFIP in hand, we present examples from the literature representing theoretical studies using HFIP as a solvent in transition metal-, Lewis/Brønsted acid-catalyzed reactions, and homogeneous catalytic reactions (with HFIP itself acting as a catalyst. These examples emphasize the multifunctional role played by HFIP. This indicates that in-depth understanding of its reaction mechanism and performance characteristics is helpful to optimize its application conditions in organic synthesis and improve the efficiency and yield of the reaction. The deep theoretical studies of HFIP in chemical reactions is expected to provide more possibilities and selectivity for the synthesis and application of new compounds.
{"title":"Research progress of homogeneous catalytic reactions of hexafluoroisopropanol (HFIP)","authors":"Huiying Xu, Huidan Luo, Yi Wang, Hui Gao","doi":"10.1016/j.tgchem.2025.100071","DOIUrl":"10.1016/j.tgchem.2025.100071","url":null,"abstract":"<div><div>1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a solvent with unique properties. In recent years, it has received widespread attention due to its ability to stabilize ionic species, transfer protons, and participate in a range of intermolecular interactions, demonstrating excellent benefits in facilitating a variety of challenging chemical reactions. In this review, after a brief introduction to the physical and chemical properties of HFIP in hand, we present examples from the literature representing theoretical studies using HFIP as a solvent in transition metal-, Lewis/Brønsted acid-catalyzed reactions, and homogeneous catalytic reactions (with HFIP itself acting as a catalyst. These examples emphasize the multifunctional role played by HFIP. This indicates that in-depth understanding of its reaction mechanism and performance characteristics is helpful to optimize its application conditions in organic synthesis and improve the efficiency and yield of the reaction. The deep theoretical studies of HFIP in chemical reactions is expected to provide more possibilities and selectivity for the synthesis and application of new compounds.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100071"},"PeriodicalIF":0.0,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143550884","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}
Pub Date : 2025-02-22DOI: 10.1016/j.tgchem.2025.100069
M. Corti , S. Princiotto , M. Zuccolo , G. Beretta , S. Dallavalle , A. Pinto , F. Annunziata , G. Borgonovo
Saffron is the most expensive spice, appreciated in the best cuisine all over the world. However, its production is connected to the generation of a high volume of waste, i.e. stamens, leaves, tepals, spathes, corm, and tunics. Several biologically active compounds and high value chemical have been identified in the saffron biomass extracts, among which is found 3-hydroxy-γ-butyrolactone (3-HBL), a chiral building block involved in the production of different active pharmaceutical ingredients. The development of the first green and scalable extractive methodology for the isolation of 3-HBL from saffron tepals and stamen could be of great interest for different chemical sectors. After the selection of the best extractive medium (ethyl acetate) and the optimization of the operative procedure to a two-step protocol, microwave assisted extraction and accelerated solvent extraction were compared. The results showed a 3.6 ± 0.2 % vs 2.1 ± 0.1 % w/w recovery and could be exploitable not only on a lab scale but also for a possible industrial application. An enantiomeric excess of 14 % of the (S)-(−) isomer was found.
{"title":"Valorization of saffron waste as a natural source of 3-hydroxy-γ-butyrolactone, a valuable chiral building block for pharmaceutical applications","authors":"M. Corti , S. Princiotto , M. Zuccolo , G. Beretta , S. Dallavalle , A. Pinto , F. Annunziata , G. Borgonovo","doi":"10.1016/j.tgchem.2025.100069","DOIUrl":"10.1016/j.tgchem.2025.100069","url":null,"abstract":"<div><div>Saffron is the most expensive spice, appreciated in the best cuisine all over the world. However, its production is connected to the generation of a high volume of waste, i.e. stamens, leaves, tepals, spathes, corm, and tunics. Several biologically active compounds and high value chemical have been identified in the saffron biomass extracts, among which is found 3-hydroxy-γ-butyrolactone (3-HBL), a chiral building block involved in the production of different active pharmaceutical ingredients. The development of the first green and scalable extractive methodology for the isolation of 3-HBL from saffron tepals and stamen could be of great interest for different chemical sectors. After the selection of the best extractive medium (ethyl acetate) and the optimization of the operative procedure to a two-step protocol, microwave assisted extraction and accelerated solvent extraction were compared. The results showed a 3.6 ± 0.2 % vs 2.1 ± 0.1 % w/w recovery and could be exploitable not only on a lab scale but also for a possible industrial application. An enantiomeric excess of 14 % of the (<em>S</em>)-(−) isomer was found.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100069"},"PeriodicalIF":0.0,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488713","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}
Pub Date : 2025-02-22DOI: 10.1016/j.tgchem.2025.100070
Miguel A. Bárbara , Nuno R. Candeias , Luis F. Veiros , Filipe Menezes , Andrea Gualandi , Pier G. Cozzi , Carlos A.M. Afonso
This study presents a novel and environmentally friendly approach to the preparation of quinic acid-derived esters from photocatalyzed O-arylation with haloarenes. This study expands the quinic acid-derived chemical space from renewable biomass by harnessing the power of visible-light-driven photocatalysis under mild conditions without the need for protecting groups. A thorough screening of reaction conditions, including the choice of photocatalyst, solvent, base, nickel source, and ligand, led to the identification of the most effective conditions, these being 5CzBN as the optimal photocatalyst, and glyme-based nickel complexes as the preferred nickel source. These conditions enabled the formation of O-arylated products with good yields without noticeable formation of decarboxylated products. Computational calculations support the proposed mechanism for the O-arylation process, based on oxidative addition, anion exchange, and reductive elimination upon energy transfer from the photocatalyst to the Ni(II) species. Computational considerations for a nickel-catalyzed photodecarboxylative arylation mechanism suggest that the oxidation of quinate by the excited photocatalyst or other species derived thereof is considerably less favorable than a pathway only involving energy transfer to a nickel species. The research provides valuable insights into the mechanism of this environmentally conscious transformation.
{"title":"Protecting group-free photocatalyzed O-arylation of quinic acid","authors":"Miguel A. Bárbara , Nuno R. Candeias , Luis F. Veiros , Filipe Menezes , Andrea Gualandi , Pier G. Cozzi , Carlos A.M. Afonso","doi":"10.1016/j.tgchem.2025.100070","DOIUrl":"10.1016/j.tgchem.2025.100070","url":null,"abstract":"<div><div>This study presents a novel and environmentally friendly approach to the preparation of quinic acid-derived esters from photocatalyzed <em>O</em>-arylation with haloarenes. This study expands the quinic acid-derived chemical space from renewable biomass by harnessing the power of visible-light-driven photocatalysis under mild conditions without the need for protecting groups. A thorough screening of reaction conditions, including the choice of photocatalyst, solvent, base, nickel source, and ligand, led to the identification of the most effective conditions, these being 5CzBN as the optimal photocatalyst, and glyme-based nickel complexes as the preferred nickel source. These conditions enabled the formation of <em>O</em>-arylated products with good yields without noticeable formation of decarboxylated products. Computational calculations support the proposed mechanism for the <em>O</em>-arylation process, based on oxidative addition, anion exchange, and reductive elimination upon energy transfer from the photocatalyst to the Ni(II) species. Computational considerations for a nickel-catalyzed photodecarboxylative arylation mechanism suggest that the oxidation of quinate by the excited photocatalyst or other species derived thereof is considerably less favorable than a pathway only involving energy transfer to a nickel species. The research provides valuable insights into the mechanism of this environmentally conscious transformation.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100070"},"PeriodicalIF":0.0,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563344","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}
The electrosynthesis of benzimidazole-fused quinazolinones from N-substituted o-phenylenediamines and isothiocyanates via a cascade addition-desulfurization-cyclization process was introduced. This electrochemical approach utilizes the mild and efficient non-metal oxidizing agent, NaI in sub-stoichiometric amounts as an electrolyte/mediator under open-flask conditions. A variety of benzimidazole-fused quinazolinones were prepared in moderate to excellent yields (30–98 %, 10 examples). Additionally, the optimal conditions were successfully applied to the synthesis of benzoxazoloquinazolinones and benzothiazolquinazolinones (30–72 %, 6 examples). This electrochemical process is scalable, while maintaining reaction efficiency even at the gram scale.
{"title":"Electrosynthesis of benzimidazole-fused quinazolinones via a cascade addition-desulfurization-cyclization process","authors":"Khuyen Thu Nguyen , Mongkol Sukwattanasinitt , Sumrit Wacharasindhu","doi":"10.1016/j.tgchem.2025.100068","DOIUrl":"10.1016/j.tgchem.2025.100068","url":null,"abstract":"<div><div>The electrosynthesis of benzimidazole-fused quinazolinones from <em>N</em>-substituted <em>o</em>-phenylenediamines and isothiocyanates <em>via</em> a cascade addition-desulfurization-cyclization process was introduced. This electrochemical approach utilizes the mild and efficient non-metal oxidizing agent, NaI in sub-stoichiometric amounts as an electrolyte/mediator under open-flask conditions. A variety of benzimidazole-fused quinazolinones were prepared in moderate to excellent yields (30–98 %, 10 examples). Additionally, the optimal conditions were successfully applied to the synthesis of benzoxazoloquinazolinones and benzothiazolquinazolinones (30–72 %, 6 examples). This electrochemical process is scalable, while maintaining reaction efficiency even at the gram scale.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100068"},"PeriodicalIF":0.0,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386522","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}
Pub Date : 2025-02-05DOI: 10.1016/j.tgchem.2025.100067
Sumanjali Kota , Akshay Shivashankar , Tushvitha Dhayakaran , Uthkruthi Munegowda , Bharath K. Devendra
This study presents a straightforward, cost-effective method for synthesizing Tin Sulfide (SnS2) nanoparticles using magnetic stirring. The prepared SnS2 was analyzed using XRD, FESEM, EDAX, UV–Vis, FTIR, XPS, HRTEM, and SAED analysis. The photodegradation of Methyl Violet (MV) dye achieved a 93.8 % decolourization rate within 120 min, following first-order kinetic reaction rates. The half-life (t1/2) was determined to be 31.18 min, and the stability of the photocatalyst was evaluated under different pH conditions. Cyclic Voltammetry (CV) studies were performed using a carbon paste electrode in 2 M KOH, revealing a low electrochemical value and proton diffusion coefficient for SnS2, indicating good redox behaviour with a Csp of approximately 158 F/g. The electrochemical sensing of urea demonstrated excellent performance with the SnS2 electrode. Additionally, the sensor's pH response was investigated under three different pH conditions, showing remarkable urea sensing capabilities influenced by pH and electrolyte environment.
本研究提出了一种利用磁搅拌合成硫化锡（SnS2）纳米粒子的简单、经济的方法。采用XRD、FESEM、EDAX、UV-Vis、FTIR、XPS、HRTEM、SAED等分析方法对制备的SnS2进行了表征。甲基紫（MV）染料在120 min内脱色率达到93.8%，符合一级动力学反应速率。半衰期（t1/2）为31.18 min，并对不同pH条件下光催化剂的稳定性进行了评价。循环伏安法（CV）研究表明，碳膏电极在2 M KOH中具有较低的电化学值和质子扩散系数，表明SnS2具有良好的氧化还原行为，Csp约为158 F/g。SnS2电极对尿素的电化学传感性能优异。此外，研究了该传感器在三种不同pH条件下的pH响应，显示出受pH和电解质环境影响的显著尿素传感能力。
{"title":"Synthesis and characterization of SnS2 nanoparticles for enhanced photocatalytic and electrochemical sensing applications","authors":"Sumanjali Kota , Akshay Shivashankar , Tushvitha Dhayakaran , Uthkruthi Munegowda , Bharath K. Devendra","doi":"10.1016/j.tgchem.2025.100067","DOIUrl":"10.1016/j.tgchem.2025.100067","url":null,"abstract":"<div><div>This study presents a straightforward, cost-effective method for synthesizing Tin Sulfide (SnS<sub>2</sub>) nanoparticles using magnetic stirring. The prepared SnS<sub>2</sub> was analyzed using XRD, FESEM, EDAX, UV–Vis, FTIR, XPS, HRTEM, and SAED analysis. The photodegradation of Methyl Violet (MV) dye achieved a 93.8 % decolourization rate within 120 min, following first-order kinetic reaction rates. The half-life (t1/2) was determined to be 31.18 min, and the stability of the photocatalyst was evaluated under different pH conditions. Cyclic Voltammetry (CV) studies were performed using a carbon paste electrode in 2 M KOH, revealing a low electrochemical value and proton diffusion coefficient for SnS<sub>2</sub>, indicating good redox behaviour with a C<sub>sp</sub> of approximately 158 F/g. The electrochemical sensing of urea demonstrated excellent performance with the SnS<sub>2</sub> electrode. Additionally, the sensor's pH response was investigated under three different pH conditions, showing remarkable urea sensing capabilities influenced by pH and electrolyte environment.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100067"},"PeriodicalIF":0.0,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386521","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}
Synthesis of quaternary malononitriles with an aryl substituent is of great importance because these scaffolds serve as essential intermediates in the synthesis of bioactive compounds. This study presents an efficient method for the laccase-catalyzed arylation of 2-substituted malononitrile derivatives by oxidation of catechols using aerial oxygen as the oxidant, followed by the nucleophilic addition of 2-substituted malononitriles. The process achieves yields ranging from moderate to excellent (73–97 %), and also, it was associated with a slight decrease in efficiency in higher scales.
{"title":"Laccase cataylzed synthesis of quaternary malononitriles with an aryl substituent","authors":"Parisa Amani, Mansour Shahedi, Elaheh Rezaei, Zohreh Habibi","doi":"10.1016/j.tgchem.2025.100066","DOIUrl":"10.1016/j.tgchem.2025.100066","url":null,"abstract":"<div><div>Synthesis of quaternary malononitriles with an aryl substituent is of great importance because these scaffolds serve as essential intermediates in the synthesis of bioactive compounds. This study presents an efficient method for the laccase-catalyzed arylation of 2-substituted malononitrile derivatives by oxidation of catechols using aerial oxygen as the oxidant, followed by the nucleophilic addition of 2-substituted malononitriles. The process achieves yields ranging from moderate to excellent (73–97 %), and also, it was associated with a slight decrease in efficiency in higher scales.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100066"},"PeriodicalIF":0.0,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143096432","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}
Pub Date : 2025-01-25DOI: 10.1016/j.tgchem.2025.100065
Satyaranjan Behera
Nanomaterials have piqued researchers' interest in various fields due to their extraordinary advantages, which include a large surface area. The use of nanomaterials in catalysis is a hot issue for researchers. Catalysis plays a vital role in the synthesis of medicinal as well as pharmaceutical compounds. Pharmaceutical chemicals, including β-amino carbonyl compounds and their derivatives, are commonly used as synthetic intermediates in manufacturing natural products, pharmaceuticals, physiologically active molecules, and medicines. Synthesis of β-amino carbonyl compounds involves many processes, including Mannich and aza-Michael reactions. The synthesis of β-amino carbonyl compounds remains challenging for chemists due to their severe side products. Researchers have now used nanocatalysts to achieve clean and smooth reactions, high purity of products, and reusability. Due to high surface area, nanocatalysts have tremendous catalytic activity. Nowadays many modified nanocatalyst have been developed to produce high yields of the products. The present review described the synthesis of β-amino carbonyl compounds by using different nanocatalysts reported to date.
{"title":"A review on synthesis of β-amino carbonyl compounds using nanocatalyst","authors":"Satyaranjan Behera","doi":"10.1016/j.tgchem.2025.100065","DOIUrl":"10.1016/j.tgchem.2025.100065","url":null,"abstract":"<div><div>Nanomaterials have piqued researchers' interest in various fields due to their extraordinary advantages, which include a large surface area. The use of nanomaterials in catalysis is a hot issue for researchers. Catalysis plays a vital role in the synthesis of medicinal as well as pharmaceutical compounds. Pharmaceutical chemicals, including β-amino carbonyl compounds and their derivatives, are commonly used as synthetic intermediates in manufacturing natural products, pharmaceuticals, physiologically active molecules, and medicines. Synthesis of β-amino carbonyl compounds involves many processes, including Mannich and aza-Michael reactions. The synthesis of β-amino carbonyl compounds remains challenging for chemists due to their severe side products. Researchers have now used nanocatalysts to achieve clean and smooth reactions, high purity of products, and reusability. Due to high surface area, nanocatalysts have tremendous catalytic activity. Nowadays many modified nanocatalyst have been developed to produce high yields of the products. The present review described the synthesis of β-amino carbonyl compounds by using different nanocatalysts reported to date.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100065"},"PeriodicalIF":0.0,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143096509","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}
Pub Date : 2025-01-18DOI: 10.1016/j.tgchem.2025.100064
Zhuo Wang
Macrocyclic natural products present as essential scaffolds in drug development. Excited by the biological properties of macrocyclic natural products, its synthesis and the development of macrocyclization methods is an important research area in organic and medicinal chemistry. In particular, macrocyclization preparing macrocyclic structures via catalytic functionalization of unactivated C(sp3)-H bonds is increasingly prevalent in the literature. Here, we provide a minireview highlighting the contemporary advancements of catalytic macrocyclization of unactivated C(sp3)-H bond in method developments and natural product synthesis. Representative examples from 2017 to 2024 are discussed.
{"title":"Catalytic macrocyclization of unactivated C(sp3)-H bond in natural product synthesis","authors":"Zhuo Wang","doi":"10.1016/j.tgchem.2025.100064","DOIUrl":"10.1016/j.tgchem.2025.100064","url":null,"abstract":"<div><div>Macrocyclic natural products present as essential scaffolds in drug development. Excited by the biological properties of macrocyclic natural products, its synthesis and the development of macrocyclization methods is an important research area in organic and medicinal chemistry. In particular, macrocyclization preparing macrocyclic structures <em>via</em> catalytic functionalization of unactivated C(sp<sup>3</sup>)-H bonds is increasingly prevalent in the literature. Here, we provide a <em>minireview</em> highlighting the contemporary advancements of catalytic macrocyclization of unactivated C(sp<sup>3</sup>)-H bond in method developments and natural product synthesis. Representative examples from 2017 to 2024 are discussed.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100064"},"PeriodicalIF":0.0,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143096433","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}
Pub Date : 2025-01-16DOI: 10.1016/j.tgchem.2025.100063
Jens Wéry, Sofia Radelicki, Thomas J.N. Hooper, Margot Houbrechts, Kwinten Janssens, Wouter Stuyck, Dimitrios Sakellariou, Dirk E. De Vos
The atom-efficient esterification of phosphoric acid was investigated for the selective synthesis of phosphate mono-esters using an acid treated niobium oxide catalyst, avoiding the use of amines as is common in literature. Kinetic studies revealed that the heterogeneous catalyst exhibited higher selectivity for mono-esters compared to homogeneous acid catalysts, as supported by calculation of the relative reactivity of mono-ester and phosphoric acid with different catalysts. To characterize the catalyst, its Hammett acidity value (H0) was determined, while solid state 31P NMR enabled studying the adsorption of H3PO4. Due to the mild acidity of the niobium oxide, alcohols with acid-sensitive functions, including substituted double bonds, could be phosphorylated, enabling the synthesis of surfactants such as oleyl phosphate.
{"title":"Selective synthesis of phosphate mono-esters with an acidic modified niobium oxide catalyst","authors":"Jens Wéry, Sofia Radelicki, Thomas J.N. Hooper, Margot Houbrechts, Kwinten Janssens, Wouter Stuyck, Dimitrios Sakellariou, Dirk E. De Vos","doi":"10.1016/j.tgchem.2025.100063","DOIUrl":"10.1016/j.tgchem.2025.100063","url":null,"abstract":"<div><div>The atom-efficient esterification of phosphoric acid was investigated for the selective synthesis of phosphate mono-esters using an acid treated niobium oxide catalyst, avoiding the use of amines as is common in literature. Kinetic studies revealed that the heterogeneous catalyst exhibited higher selectivity for mono-esters compared to homogeneous acid catalysts, as supported by calculation of the relative reactivity of mono-ester and phosphoric acid with different catalysts. To characterize the catalyst, its Hammett acidity value (H<sub>0</sub>) was determined, while solid state <sup>31</sup>P NMR enabled studying the adsorption of H<sub>3</sub>PO<sub>4</sub>. Due to the mild acidity of the niobium oxide, alcohols with acid-sensitive functions, including substituted double bonds, could be phosphorylated, enabling the synthesis of surfactants such as oleyl phosphate.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100063"},"PeriodicalIF":0.0,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143096512","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}
Pub Date : 2025-01-02DOI: 10.1016/j.tgchem.2025.100062
Manav C. Parmar, Bonny Y. Patel
The review examines one-pot strategies and their mechanistic approaches for synthesizing the quinoline nucleus from 2009 to 2024, with a focus on their therapeutic potential. The paradigm shifts from conventional synthetic protocols to advanced green methodologies has revolutionized the synthesis of quinoline derivatives. Strategies that adhere to sustainable chemistry principles by minimizing waste, solvent consumption, and energy input. Various green catalysts, including p-toluenesulfonic acid (p-TSA), para-sulfonic acid calix[4]arene (CX4SO3H), cerium nitrate, ammonium acetate, potassium carbonate (K2CO3), and catalyst-free techniques, have proven effective in synthesizing quinoline analogs. The use of greener solvents such as ethanol and water further supports the eco-friendly synthesis of these compounds. The review also highlights a broad spectrum of pharmacological activities of quinoline derivatives, including antibacterial, antiviral, antidiabetic, anticancer properties and so on. SAR studies show that adding EDGs (-CH3, –OCH3, –OH) and EWGs (-Cl, –F, –NO2, –CF3) can enhance electronic properties, lipophilicity, and receptor-binding affinities. Moreover, hybridization with heterocyclic scaffolds such as furan, pyrazole, indole, and thiadiazole significantly improves bioactivity, demonstrating the intricate relationship between structural modifications and biological efficacy. By merging sustainable chemistry with targeted pharmacological strategies, quinoline-based compounds emerge as innovative candidates for diverse clinical applications.
{"title":"Green and traditional one-pot synthesis techniques for bioactive quinoline derivatives: A review","authors":"Manav C. Parmar, Bonny Y. Patel","doi":"10.1016/j.tgchem.2025.100062","DOIUrl":"10.1016/j.tgchem.2025.100062","url":null,"abstract":"<div><div>The review examines one-pot strategies and their mechanistic approaches for synthesizing the quinoline nucleus from 2009 to 2024, with a focus on their therapeutic potential. The paradigm shifts from conventional synthetic protocols to advanced green methodologies has revolutionized the synthesis of quinoline derivatives. Strategies that adhere to sustainable chemistry principles by minimizing waste, solvent consumption, and energy input. Various green catalysts, including <em>p</em>-toluenesulfonic acid (<em>p</em>-TSA), <em>para</em>-sulfonic acid calix[4]arene (CX4SO<sub>3</sub>H), cerium nitrate, ammonium acetate, potassium carbonate (K<sub>2</sub>CO<sub>3</sub>), and catalyst-free techniques, have proven effective in synthesizing quinoline analogs. The use of greener solvents such as ethanol and water further supports the eco-friendly synthesis of these compounds. The review also highlights a broad spectrum of pharmacological activities of quinoline derivatives, including antibacterial, antiviral, antidiabetic, anticancer properties and so on. SAR studies show that adding EDGs (-CH<sub>3</sub>, –OCH<sub>3</sub>, –OH) and EWGs (-Cl, –F, –NO<sub>2</sub>, –CF<sub>3</sub>) can enhance electronic properties, lipophilicity, and receptor-binding affinities. Moreover, hybridization with heterocyclic scaffolds such as furan, pyrazole, indole, and thiadiazole significantly improves bioactivity, demonstrating the intricate relationship between structural modifications and biological efficacy. By merging sustainable chemistry with targeted pharmacological strategies, quinoline-based compounds emerge as innovative candidates for diverse clinical applications.</div></div>","PeriodicalId":101215,"journal":{"name":"Tetrahedron Green Chem","volume":"5 ","pages":"Article 100062"},"PeriodicalIF":0.0,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135611","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}
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