Pub Date : 2026-01-29DOI: 10.1016/j.tet.2026.135160
Koichi Mizuno, Yuta Ito, Yoshiyuki Hari
2′-O,4′-C-Ethylene-bridged nucleic acid (ENA) is a promising chemical modification for oligonucleotide (ON) therapeutics. Thus, ENA analogs bearing functional groups on the ethylene bridges were designed to explore new candidates for ON therapeutics. Specifically, the phosphoramidite of 2′-O,4′-C-ethylene-bridged 5-methyluridine (ENA-T-CO2Me) bearing a methoxycarbonylmethyl group on the bridge was synthesized and it was incorporated into ONs using an automated ON synthesizer. The methoxycarbonyl moieties in the ONs were subsequently converted into carboxylic acid equivalents, such as carboxyl and carbamoyl groups, by the corresponding base treatment in a post-synthetic approach. Duplex-forming ability and nuclease stability of ONs with these ENA analogs were evaluated. Among the analogs, the carboxymethyl-substituted analog (ENA-T-CO2H) highly stabilized a duplex with single-stranded RNA and exhibited the greatest resistance to degradation by 3′-exonuclease.
2 ' -O,4 ' - c -乙烯桥接核酸（ENA）是一种很有前途的寡核苷酸（ON）治疗化学修饰。因此，在乙烯桥上携带官能团的ENA类似物被设计用于探索on治疗的新候选物。具体而言，合成了2 ' -O,4 ' - c -乙烯桥接5-甲基尿嘧啶（na - t - co2me）的磷酰胺，其桥接上有一个甲氧羰基甲基，并使用自动on合成器将其纳入on中。在合成后的方法中，通过相应的碱基处理，ONs中的甲氧羰基部分随后转化为羧酸等价物，如羧基和氨基甲酰基。评价了这些ENA类似物对离子的双工形成能力和核酸酶稳定性。在这些类似物中，羧基甲基取代类似物（ENA-T-CO2H）与单链RNA的双链高度稳定，并表现出最大的抗3 ' -外切酶降解能力。
{"title":"Synthesis and properties of oligonucleotides containing 2′-O,4′-C-ethylene-bridged 5-methyluridines bearing a functional group on the bridge","authors":"Koichi Mizuno, Yuta Ito, Yoshiyuki Hari","doi":"10.1016/j.tet.2026.135160","DOIUrl":"10.1016/j.tet.2026.135160","url":null,"abstract":"<div><div>2′-<em>O</em>,4′-<em>C</em>-Ethylene-bridged nucleic acid (ENA) is a promising chemical modification for oligonucleotide (ON) therapeutics. Thus, ENA analogs bearing functional groups on the ethylene bridges were designed to explore new candidates for ON therapeutics. Specifically, the phosphoramidite of 2′-<em>O</em>,4′-<em>C</em>-ethylene-bridged 5-methyluridine (ENA-T-CO<sub>2</sub>Me) bearing a methoxycarbonylmethyl group on the bridge was synthesized and it was incorporated into ONs using an automated ON synthesizer. The methoxycarbonyl moieties in the ONs were subsequently converted into carboxylic acid equivalents, such as carboxyl and carbamoyl groups, by the corresponding base treatment in a post-synthetic approach. Duplex-forming ability and nuclease stability of ONs with these ENA analogs were evaluated. Among the analogs, the carboxymethyl-substituted analog (ENA-T-CO<sub>2</sub>H) highly stabilized a duplex with single-stranded RNA and exhibited the greatest resistance to degradation by 3′-exonuclease.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135160"},"PeriodicalIF":2.2,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146077003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-24DOI: 10.1016/j.tet.2026.135159
Marcus M. Sá
There is an urgent need to mitigate environmental problems caused by uncontrolled human activities. The ever-increasing demand for more sustainable processes has stimulated the adoption of efficient synthetic strategies founded on the principles of green chemistry, which must be simple, safe, highly productive, and environmentally benign. Therefore, this Review showcases the most prominent achievements in the green preparation and synthetic applications of diazo compounds that were published in the last 15 years (from 2010 to middle 2025). The main approaches include the use of heterogeneous catalysis, biocatalysis, and catalyst-free protocols, the preference for water and other harmless solvents, and the search for simple and mild reaction conditions to furnish the target compounds with broad structural diversity and excellent functional group tolerance, as well as high yield and selectivity.
{"title":"Greener preparation and reactivity of diazo compounds: Moving from harmful chemistry to more environmentally benign methods","authors":"Marcus M. Sá","doi":"10.1016/j.tet.2026.135159","DOIUrl":"10.1016/j.tet.2026.135159","url":null,"abstract":"<div><div>There is an urgent need to mitigate environmental problems caused by uncontrolled human activities. The ever-increasing demand for more sustainable processes has stimulated the adoption of efficient synthetic strategies founded on the principles of green chemistry, which must be simple, safe, highly productive, and environmentally benign. Therefore, this Review showcases the most prominent achievements in the green preparation and synthetic applications of diazo compounds that were published in the last 15 years (from 2010 to middle 2025). The main approaches include the use of heterogeneous catalysis, biocatalysis, and catalyst-free protocols, the preference for water and other harmless solvents, and the search for simple and mild reaction conditions to furnish the target compounds with broad structural diversity and excellent functional group tolerance, as well as high yield and selectivity.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135159"},"PeriodicalIF":2.2,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.tet.2026.135158
Shweta A. Pawar, A. Vijay Kumar
Polydopamine (PDA) is demonstrated as a promising heterogeneous organocatalyst for the efficacious synthesis of quinazolin-4(3H)-ones employing the readily available DMSO as the methine synthon. PDA-mediated activation of DMSO in the presence of the green oxidant molecular oxygen, facilitated oxidative annulation of anthranilamides to afford quinazolin-4(3H)-one frameworks. This method enabled a broad substrate scope, with various anthranilamide derivatives and sulfoxide precursors furnishing the corresponding quinazolin-4(3H)-ones products in good to excellent yields. The mechanistic studies revealed an oxygen-mediated radical pathway for quinazolin-4(3H)-ones synthesis. The developed protocol was robustly applied to the synthesis of the bioactive alkaloid (Z)-schizocommunin and the CNS depressant drug methaqualone. PDA was efficiently recovered and recycled for up to three consecutive cycles for the quinazolin-4(3H)-ones reaction. Overall, the developed PDA-mediated protocol delivered notable advantages, including metal-free conditions, catalyst recyclability, and the avoidance of additives, co-catalysts, and peroxides, underscoring the utility of PDA as a heterogeneous organocatalyst for oxidative annulation.
{"title":"Polydopamine: A bioinspired catalyst for the metal-free synthesis of quinazolinones using DMSO as a carbon synthon","authors":"Shweta A. Pawar, A. Vijay Kumar","doi":"10.1016/j.tet.2026.135158","DOIUrl":"10.1016/j.tet.2026.135158","url":null,"abstract":"<div><div>Polydopamine (PDA) is demonstrated as a promising heterogeneous organocatalyst for the efficacious synthesis of quinazolin-4(3<em>H</em>)-ones employing the readily available DMSO as the methine synthon. PDA-mediated activation of DMSO in the presence of the green oxidant molecular oxygen, facilitated oxidative annulation of anthranilamides to afford quinazolin-4(3<em>H</em>)-one frameworks. This method enabled a broad substrate scope, with various anthranilamide derivatives and sulfoxide precursors furnishing the corresponding quinazolin-4(3<em>H</em>)-ones products in good to excellent yields. The mechanistic studies revealed an oxygen-mediated radical pathway for quinazolin-4(3<em>H</em>)-ones synthesis. The developed protocol was robustly applied to the synthesis of the bioactive alkaloid (Z)-schizocommunin and the CNS depressant drug methaqualone. PDA was efficiently recovered and recycled for up to three consecutive cycles for the quinazolin-4(3<em>H</em>)-ones reaction. Overall, the developed PDA-mediated protocol delivered notable advantages, including metal-free conditions, catalyst recyclability, and the avoidance of additives, co-catalysts, and peroxides, underscoring the utility of PDA as a heterogeneous organocatalyst for oxidative annulation.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135158"},"PeriodicalIF":2.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.tet.2026.135149
Sekar Yuvasree, Rajagopal Nagarajan
Oxidation of alcohols to the carbonyl compounds is an important and routine transformation useful in the variety of organic syntheses. Several methods have been reported for this transformation and are well documented in literature. We have discovered an unprecedented environmentally benign method for the selective oxidation of diarylmethanols to ketones and ether formation mediated by Amberlyst-15. Amberlyst-15 has been found to be selective, efficient, and recyclable, with yields obtained in the range of 20–90 %.
{"title":"Amberlyst-15 mediated unprecedented oxidation: tunability of the oxidation of diarylmethanols or ether formation","authors":"Sekar Yuvasree, Rajagopal Nagarajan","doi":"10.1016/j.tet.2026.135149","DOIUrl":"10.1016/j.tet.2026.135149","url":null,"abstract":"<div><div>Oxidation of alcohols to the carbonyl compounds is an important and routine transformation useful in the variety of organic syntheses. Several methods have been reported for this transformation and are well documented in literature. We have discovered an unprecedented environmentally benign method for the selective oxidation of diarylmethanols to ketones and ether formation mediated by Amberlyst-15. Amberlyst-15 has been found to be selective, efficient, and recyclable, with yields obtained in the range of 20–90 %.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"193 ","pages":"Article 135149"},"PeriodicalIF":2.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.tet.2026.135157
Mátyás Milen, Patrik Pollák, Balázs Volk
These days, multicomponent reactions, involving at least three reagents, are of particular interest for the reason that they ensure operational simplicity, and make possible the fast establishment of molecular libraries for biological screening. On the other hand, the use of propylphosphonic anhydride (T3P® reagent) as an activating agent in a wide range of organic reactions is an excellent tool. In this review article, the two above-mentioned disciplines are combined: the applications of the T3P® reagent in multicomponent organic chemical transformations are surveyed. The compilation embraces the synthesis of α-aminonitriles, α-aminoamides, α-aminophosphonates, isoindolinone-phosphonates, hydroxynaphthalenes and naphthoxazinones, pyrano- and furano-quinolines, quinazolinones, oxoisoindoline-carboxamides, imidazopyridines, thiazolidinones, dihydropyrimidinones and hexahydrodibenzodiazepinones. Comparisons with the previous preparative methods are also provided. Finally, the beneficial effect of the T3P® reagent is illustrated via the proposed mechanisms.
{"title":"Propylphosphonic anhydride (T3P®)-mediated multicomponent reactions","authors":"Mátyás Milen, Patrik Pollák, Balázs Volk","doi":"10.1016/j.tet.2026.135157","DOIUrl":"10.1016/j.tet.2026.135157","url":null,"abstract":"<div><div>These days, multicomponent reactions, involving at least three reagents, are of particular interest for the reason that they ensure operational simplicity, and make possible the fast establishment of molecular libraries for biological screening. On the other hand, the use of propylphosphonic anhydride (T3P® reagent) as an activating agent in a wide range of organic reactions is an excellent tool. In this review article, the two above-mentioned disciplines are combined: the applications of the T3P® reagent in multicomponent organic chemical transformations are surveyed. The compilation embraces the synthesis of α-aminonitriles, α-aminoamides, α-aminophosphonates, isoindolinone-phosphonates, hydroxynaphthalenes and naphthoxazinones, pyrano- and furano-quinolines, quinazolinones, oxoisoindoline-carboxamides, imidazopyridines, thiazolidinones, dihydropyrimidinones and hexahydrodibenzodiazepinones. Comparisons with the previous preparative methods are also provided. Finally, the beneficial effect of the T3P® reagent is illustrated via the proposed mechanisms.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"194 ","pages":"Article 135157"},"PeriodicalIF":2.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-23DOI: 10.1016/j.tet.2026.135156
Koto Tagami, Tomoko Yajima
Amines are known to form halogen bonds with perfluoroalkyl halides, enabling the formation of electron donor–acceptor (EDA) complexes. In recent years, visible light-induced radical perfluoroalkylation reactions based on halogen-bonded EDA complexes have attracted increasing attention. This review provides a comprehensive overview of perfluoroalkylation reactions mediated by amines, categorized into two major sections: reactions employing amines as external catalysts and those in which the amines themselves serve as substrates and non-catalyze reactions. In the first part, we systematically summarize the types of amines used under optimal conditions and evaluated during conditional screening. By analyzing these reports, we highlighted the trends in amine selection for effective halogen bonding with perfluoroalkyl halides and identified the amines that have proven to be successful. The second part focuses on catalyst-free systems in which amines undergo perfluoroalkylation by acting as both halogen bond acceptor and reactive substrates. These examples were further classified based on the structural type of the anime. Finally, we discuss perspectives and future directions by considering unexplored and less-studied amines and their potential to form productive halogen-bonded EDA complexes with perfluoroalkyl halides. This structure-focused review aims to serve as a guide for designing new amine–perfluoroalkyl systems and for understanding the structure–reactivity relationships that govern visible-light-induced radical processes.
{"title":"Perfluoroalkylation reactions via halogen-bonded electron donor-acceptor (EDA) complexes of amines and perfluoroalkyl halides under visible light","authors":"Koto Tagami, Tomoko Yajima","doi":"10.1016/j.tet.2026.135156","DOIUrl":"10.1016/j.tet.2026.135156","url":null,"abstract":"<div><div>Amines are known to form halogen bonds with perfluoroalkyl halides, enabling the formation of electron donor–acceptor (EDA) complexes. In recent years, visible light-induced radical perfluoroalkylation reactions based on halogen-bonded EDA complexes have attracted increasing attention. This review provides a comprehensive overview of perfluoroalkylation reactions mediated by amines, categorized into two major sections: reactions employing amines as external catalysts and those in which the amines themselves serve as substrates and non-catalyze reactions. In the first part, we systematically summarize the types of amines used under optimal conditions and evaluated during conditional screening. By analyzing these reports, we highlighted the trends in amine selection for effective halogen bonding with perfluoroalkyl halides and identified the amines that have proven to be successful. The second part focuses on catalyst-free systems in which amines undergo perfluoroalkylation by acting as both halogen bond acceptor and reactive substrates. These examples were further classified based on the structural type of the anime. Finally, we discuss perspectives and future directions by considering unexplored and less-studied amines and their potential to form productive halogen-bonded EDA complexes with perfluoroalkyl halides. This structure-focused review aims to serve as a guide for designing new amine–perfluoroalkyl systems and for understanding the structure–reactivity relationships that govern visible-light-induced radical processes.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"193 ","pages":"Article 135156"},"PeriodicalIF":2.2,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.tet.2026.135150
Ligia Breda e Vasconcelos , Samuel Filipe Cardoso de Paula , Pedro Henrique de Oliveira Santiago , Javier Ellena , André Luiz Meleiro Porto
- In this work, the green synthesis method based on the bio-oxidation of progesterone was investigated using the mycelium of the marine-origin fungus, Penicillium oxalicum CBMAI 1996. The structural characterization of a novel minor product, 2β,15β-dihydroxyprogesterone (2β,15β-di-OH), was carried out using NMR techniques (1D, 1H and 13C; 2D, HSQC, HMBC, COSY, and NOESY), FTIR, and single crystal X-ray diffraction. The biotransformation reactions of progesterone to obtain the compound 2β,15β-di-OH were carried out in quintuplicate over 15 days (32 °C, 130 rpm, pH 7.4). Furthermore, the novel X-ray single crystal analyses of the major products, 15β-hydroxyprogesterone (15β-OH) and 7β,15β-dihydroxyprogesterone (7β,15β-di-OH), which were also previously isolated from the fungus P. oxalicum CBMAI 1996, unequivocally confirmed their structural formulas. It was also possible to determine from the X-ray analyses the absolute configuration of the hydroxylated chiral carbons, so the obtained values were 15R–OH, 7S,15R-di-OH, and 2S,15R-di-OH.
{"title":"A novel progesterone product obtained by biooxidation from marine-derivated fungus Penicillium oxalicum CBMAI 1996","authors":"Ligia Breda e Vasconcelos , Samuel Filipe Cardoso de Paula , Pedro Henrique de Oliveira Santiago , Javier Ellena , André Luiz Meleiro Porto","doi":"10.1016/j.tet.2026.135150","DOIUrl":"10.1016/j.tet.2026.135150","url":null,"abstract":"<div><div>- In this work, the green synthesis method based on the bio-oxidation of progesterone was investigated using the mycelium of the marine-origin fungus, <em>Penicillium oxalicum</em> CBMAI 1996. The structural characterization of a novel minor product, <strong>2β,15β-dihydroxyprogesterone</strong> (<strong>2β,15β-di-OH</strong>), was carried out using NMR techniques (1D, <sup>1</sup>H and <sup>13</sup>C; 2D, HSQC, HMBC, COSY, and NOESY), FTIR, and single crystal X-ray diffraction. The biotransformation reactions of progesterone to obtain the compound <strong>2β,15β-di-OH</strong> were carried out in quintuplicate over 15 days (32 °C, 130 rpm, pH 7.4). Furthermore, the novel X-ray single crystal analyses of the major products, <strong>15β-hydroxyprogesterone</strong> (<strong>15β-OH</strong>) and <strong>7β,15β-dihydroxyprogesterone</strong> (<strong>7β,15β-di-OH</strong>), which were also previously isolated from the fungus <em>P. oxalicum</em> CBMAI 1996, unequivocally confirmed their structural formulas. It was also possible to determine from the X-ray analyses the absolute configuration of the hydroxylated chiral carbons, so the obtained values were 15<em>R</em>–OH, 7<em>S</em>,15<em>R</em>-di-OH, and 2<em>S</em>,15<em>R</em>-di-OH.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"193 ","pages":"Article 135150"},"PeriodicalIF":2.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-19DOI: 10.1016/j.tet.2026.135154
Peipei Ma, Yuan Wang, Haifeng Gan, Jianliang Zhu
A novel protocol of TFA-mediated oxidative coupling of quinoxalinones with 5-pyrazolones to prepare 4-quinoxalinon-pyrazolones has been realized under air. The protocol was carried out under metal-free conditions and the reactions proceeded in moderate to excellent yields. This protocol can be applied to the efficient synthesis of quinoxalinone drug analogs. Mechanistic investigation suggested that ionic pathway exists and TFA plays an important role in the formation of the products.
{"title":"TFA-mediated oxidative dehydrogenative coupling of quinoxalinones with edaravone and its analogs","authors":"Peipei Ma, Yuan Wang, Haifeng Gan, Jianliang Zhu","doi":"10.1016/j.tet.2026.135154","DOIUrl":"10.1016/j.tet.2026.135154","url":null,"abstract":"<div><div>A novel protocol of TFA-mediated oxidative coupling of quinoxalinones with 5-pyrazolones to prepare 4-quinoxalinon-pyrazolones has been realized under air. The protocol was carried out under metal-free conditions and the reactions proceeded in moderate to excellent yields. This protocol can be applied to the efficient synthesis of quinoxalinone drug analogs. Mechanistic investigation suggested that ionic pathway exists and TFA plays an important role in the formation of the products.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"193 ","pages":"Article 135154"},"PeriodicalIF":2.2,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the study, we report a dearomative (3 + 2) cycloaddition reaction between pyrrolidinone-based Morita-Baylis-Hillman (MBH) carbonates and isoquinolines. The reaction represents an effective strategy for the rapid formation of the biologically significant and structurally complex spiropyrrolidine-fused pyrrolo[2,1-a]isoquinoline core in high yields (up to 99 % yields) with excellent regio- and diastereoselectivities (in all cases, >25:1 dr) in a single step without the requirement for any catalysts. Moreover, the synthetic utility of this approach is further demonstrated through scale-up reactions and synthetic transformations of the resulting products. Additionally, molecular docking studies have unveiled that the novel spiroheterocyclic privileged structures, which integrate pyrrolidine and pyrrolo[2,1-a]isoquinoline moieties, hold potential antiparasitic activity.
{"title":"Highly regio- and diastereoselective synthesis of spiropyrrolidine-fused pyrrolo[2,1-a]isoquinolines through dearomative (3 + 2) cycloaddition reactions","authors":"Kai-Kai Wang, Liang-Man Wu, Bo-Wen Zhang, Yi-Fan Zhang, Yu Tang, Si-Qi Wei, Yan-Rui Ma, Guo-Yi Yan, Rongxiang Chen","doi":"10.1016/j.tet.2026.135155","DOIUrl":"10.1016/j.tet.2026.135155","url":null,"abstract":"<div><div>In the study, we report a dearomative (3 + 2) cycloaddition reaction between pyrrolidinone-based Morita-Baylis-Hillman (MBH) carbonates and isoquinolines. The reaction represents an effective strategy for the rapid formation of the biologically significant and structurally complex spiropyrrolidine-fused pyrrolo[2,1-<em>a</em>]isoquinoline core in high yields (up to 99 % yields) with excellent regio- and diastereoselectivities (in all cases, >25:1 dr) in a single step without the requirement for any catalysts. Moreover, the synthetic utility of this approach is further demonstrated through scale-up reactions and synthetic transformations of the resulting products. Additionally, molecular docking studies have unveiled that the novel spiroheterocyclic privileged structures, which integrate pyrrolidine and pyrrolo[2,1-<em>a</em>]isoquinoline moieties, hold potential antiparasitic activity.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"193 ","pages":"Article 135155"},"PeriodicalIF":2.2,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023267","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A mild and cost-effective cobalt-catalyzed anti-Markovnikov-selective hydrosilylation of perfluoroalkylethylenes has been developed. This procedure facilitates the synthesis of linear perfluoroalkylethylated silane derivatives with high site selectivity, chemoselectivity, and catalytic efficiency. The practicality of this approach is further demonstrated by its successful application in large-scale reactions and the conversion of the synthesized perfluoroalkylethylated silane derivatives into 2-perfluoroalkyl ethanol.
{"title":"Cobalt-catalyzed anti-Markovnikov-selective hydrosilylation of perfluoroalkylethylenes to access perfluoroalkylethylated silane derivatives","authors":"Huiqin Wei , Renning Dong , Yangjie Huang , Zhiqiang Weng , Fang Ke","doi":"10.1016/j.tet.2026.135151","DOIUrl":"10.1016/j.tet.2026.135151","url":null,"abstract":"<div><div>A mild and cost-effective cobalt-catalyzed <em>anti</em>-Markovnikov-selective hydrosilylation of perfluoroalkylethylenes has been developed. This procedure facilitates the synthesis of linear perfluoroalkylethylated silane derivatives with high site selectivity, chemoselectivity, and catalytic efficiency. The practicality of this approach is further demonstrated by its successful application in large-scale reactions and the conversion of the synthesized perfluoroalkylethylated silane derivatives into 2-perfluoroalkyl ethanol.</div></div>","PeriodicalId":437,"journal":{"name":"Tetrahedron","volume":"193 ","pages":"Article 135151"},"PeriodicalIF":2.2,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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