Priyanka Nath , Mohit L. Deb , Jayanta Kumar Nath , Pranjal K. Baruah
This study presents a sustainable and efficient visible‐light‐driven organophotocatalytic strategy for transforming the methylene carbon of barbituric acids into valuable hydrazones and spirocyclic products. The reaction proceeds smoothly under mild conditions by utilizing eosin Y as a green photocatalyst and atmospheric oxygen as the sole oxidant. This method provides an environmentally friendly alternative to traditional approaches and offers intriguing mechanistic insights into umpolung C(sp3)‐H functionalization, thereby paving the way for novel reactivity in barbiturate chemistry.
{"title":"Visible Light‐induced Organophotocatalytic Umpolung C(sp3)‐H Functionalization of Barbituric Acids","authors":"Priyanka Nath , Mohit L. Deb , Jayanta Kumar Nath , Pranjal K. Baruah","doi":"10.1002/ajoc.70226","DOIUrl":"10.1002/ajoc.70226","url":null,"abstract":"<div><div>This study presents a sustainable and efficient visible‐light‐driven organophotocatalytic strategy for transforming the methylene carbon of barbituric acids into valuable hydrazones and spirocyclic products. The reaction proceeds smoothly under mild conditions by utilizing eosin Y as a green photocatalyst and atmospheric oxygen as the sole oxidant. This method provides an environmentally friendly alternative to traditional approaches and offers intriguing mechanistic insights into umpolung C(sp3)‐H functionalization, thereby paving the way for novel reactivity in barbiturate chemistry.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e70226"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The tricyclic ketal scaffold, found in bioactive natural products such as bullataketals A/B, represents a synthetically challenging yet pharmacologically important structural motif. The detailed mechanism to construct the tricyclic ketal core and mechanistic basis for its regioselectivity are unresolved. Here, we employ density functional theory (DFT) calculations to elucidate the plausible reaction pathways and rationalize the observed product distribution. Potential energy surface (PES) analysis reveals the critical intermediates and transition states governing the cycloaddition, and evaluation of the competing transition states demonstrates the regioselectivity of the reaction. Our computational study validates the proposed biosynthetic hypothesis, offering valuable insights for the synthesis design of complex tricyclic ketal core‐containing natural products.
{"title":"Theoretical Studies on Construction of Tricyclic Ketal Core of Bullataketals Through a Biomimetic Intermolecular (3+3) Type Cycloaddition","authors":"Dr. Ping Chen , Qi‐Feng Wang , Dr. Kai Chen","doi":"10.1002/ajoc.70238","DOIUrl":"10.1002/ajoc.70238","url":null,"abstract":"<div><div>The tricyclic ketal scaffold, found in bioactive natural products such as bullataketals <strong>A</strong>/<strong>B</strong>, represents a synthetically challenging yet pharmacologically important structural motif. The detailed mechanism to construct the tricyclic ketal core and mechanistic basis for its regioselectivity are unresolved. Here, we employ density functional theory (DFT) calculations to elucidate the plausible reaction pathways and rationalize the observed product distribution. Potential energy surface (PES) analysis reveals the critical intermediates and transition states governing the cycloaddition, and evaluation of the competing transition states demonstrates the regioselectivity of the reaction. Our computational study validates the proposed biosynthetic hypothesis, offering valuable insights for the synthesis design of complex tricyclic ketal core‐containing natural products.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e70238"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
β‐nitro ketones represent highly significant compounds for their simultaneous nucleophilic and electrophilic reactive sites in 1,3‐related positions. These molecules are commonly obtained via nitration of enones in aprotic apolar organic solvents (such as THF and CPME) with large excesses of nitrating agents and acetic acid. In this work the use of weakly acidic natural deep eutectic solvents (NADESs) – glycolic acid based‐ones – is proposed as both green and catalytic reaction media for the nitration of enones giving β‐nitro ketones. The NADESs mixtures employed were the ones formed by mixing glycolic acid with trimethylglycine, with choline chloride and with water. The reaction proceeded with stochiometric amounts of nitration agents and taking advantage from the catalytic behavior of the NADESs solvents; the scope was explored giving satisfactory yields.
{"title":"Glycolic Acid‐Based Natural Deep Eutectic Solvents (NADESs) as Catalytic Reaction Media for the Synthesis of β‐Nitro Ketones","authors":"Dario Gentili , Enrico Marcantoni , Gabriele Lupidi , Alessandro Palmieri , Matteo Tiecco","doi":"10.1002/ajoc.70234","DOIUrl":"10.1002/ajoc.70234","url":null,"abstract":"<div><div>β‐nitro ketones represent highly significant compounds for their simultaneous nucleophilic and electrophilic reactive sites in 1,3‐related positions. These molecules are commonly obtained via nitration of enones in aprotic apolar organic solvents (such as THF and CPME) with large excesses of nitrating agents and acetic acid. In this work the use of weakly acidic natural deep eutectic solvents (NADESs) – glycolic acid based‐ones – is proposed as both green and catalytic reaction media for the nitration of enones giving β‐nitro ketones. The NADESs mixtures employed were the ones formed by mixing glycolic acid with trimethylglycine, with choline chloride and with water. The reaction proceeded with stochiometric amounts of nitration agents and taking advantage from the catalytic behavior of the NADESs solvents; the scope was explored giving satisfactory yields.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e70234"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Liwen Lu , Tianlun Zhou , Hongmei Luo , YuXin Ding , Prof. Weike Su , Changjun Zhang , Prof. Yuanyuan Xie
We have successfully developed a photocatalytic radical cascade cyclization reaction for the efficient synthesis of tetrahydroquinoline derivatives with diverse structural variations. This method enables the one‐pot synthesis of tetrahydroquinolines with high yields, offering a valuable strategy for construction of C(sp3)─CH2CF3containing molecules. The approach features low catalyst load, excellent regioselectivity, and a broad substrate scope, all under mild reaction conditions. Furthermore, the selectivity for mono‐ and di‐trifluoromethylated products can be fine‐tuned by adjusting the amount of Togni's reagent II and the choice of solvent.
{"title":"Visible‐Light Driven Radical Cyclization Strategy for C(sp3)─CH2CF3─Functional Tetrahydroquinoline Derivatives","authors":"Liwen Lu , Tianlun Zhou , Hongmei Luo , YuXin Ding , Prof. Weike Su , Changjun Zhang , Prof. Yuanyuan Xie","doi":"10.1002/ajoc.70217","DOIUrl":"10.1002/ajoc.70217","url":null,"abstract":"<div><div>We have successfully developed a photocatalytic radical cascade cyclization reaction for the efficient synthesis of tetrahydroquinoline derivatives with diverse structural variations. This method enables the one‐pot synthesis of tetrahydroquinolines with high yields, offering a valuable strategy for construction of C(sp<sup>3</sup>)─CH<sub>2</sub>CF<sub>3</sub>containing molecules. The approach features low catalyst load, excellent regioselectivity, and a broad substrate scope, all under mild reaction conditions. Furthermore, the selectivity for mono‐ and di‐trifluoromethylated products can be fine‐tuned by adjusting the amount of Togni's reagent II and the choice of solvent.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e70217"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753699","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Vishal Sharma , Anjali Chaturvedi , Dr. Chandi C. Malakar , Dr. Ravindra K. Rawal , Dr. Manpreet Singh , Prof. Virender Singh
This study presents an efficient chemoselective synthesis of a series of Y‐shaped cross‐conjugated triethynylethylenes. The rapid synthesis of these densely conjugated triethynylethylenes was achieved in a short reaction time of 1–1.5 h through dual Sonogashira cross‐coupling of bifunctional 4,4‐dibromobut‐3‐en‐1‐ynes with terminal alkynes under ambient conditions. This method proved highly effective for gram‐scale synthesis, yielding a library of 58 triethynylethylenes with good to excellent yields (upto 98%). It was found that the generated triethynylethylenes were amenable to late‐stage functionalization via Heck reaction and could also be subjected to annulation reactions to furnish polycyclic aromatic hydrocarbons (PAHs). The process operates under mild reaction conditions in short reaction time, avoids the use of hazardous alkynyl metal reagents, and supports a wide range of substrates.
{"title":"Modular Synthesis of Cross‐Conjugated Triethynylethylenes via Double Sonogashira Coupling: A Platform for π‐Extended Frameworks","authors":"Vishal Sharma , Anjali Chaturvedi , Dr. Chandi C. Malakar , Dr. Ravindra K. Rawal , Dr. Manpreet Singh , Prof. Virender Singh","doi":"10.1002/ajoc.70225","DOIUrl":"10.1002/ajoc.70225","url":null,"abstract":"<div><div>This study presents an efficient chemoselective synthesis of a series of Y‐shaped cross‐conjugated triethynylethylenes. The rapid synthesis of these densely conjugated triethynylethylenes was achieved in a short reaction time of 1–1.5 h through dual Sonogashira cross‐coupling of bifunctional 4,4‐dibromobut‐3‐en‐1‐ynes with terminal alkynes under ambient conditions. This method proved highly effective for gram‐scale synthesis, yielding a library of 58 triethynylethylenes with good to excellent yields (upto 98%). It was found that the generated triethynylethylenes were amenable to late‐stage functionalization via Heck reaction and could also be subjected to annulation reactions to furnish polycyclic aromatic hydrocarbons (PAHs). The process operates under mild reaction conditions in short reaction time, avoids the use of hazardous alkynyl metal reagents, and supports a wide range of substrates.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e70225"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Asymmetric organocatalysis is an extremely powerful tool for the synthesis of diverse chiral cyclic systems including carbo and heterocycles. Various types of heterocycles containing Sulfur atom have also been synthesized including fused polycycles, spirocycles, axially chiral motifs etc. by advent of using chiral organocatalysts. Both covalent and non‐covalent activation have been explored by different organocatalysts to execute multistep cascade processes for facile access of interesting molecular architectures containing Sulfur atom. Present review documents the different avenues of organocatalysis for the asymmetric synthesis of thiacycles from 2010 onward. The article has been segmented by the nature of organocatalyst used and special attention has been put on the mechanistic rationale of the process to understand the stereochemical output.
{"title":"Organocatalyzed Asymmetric Synthesis of Thiacycles","authors":"Dr. Anup Biswas","doi":"10.1002/ajoc.70218","DOIUrl":"10.1002/ajoc.70218","url":null,"abstract":"<div><div>Asymmetric organocatalysis is an extremely powerful tool for the synthesis of diverse chiral cyclic systems including carbo and heterocycles. Various types of heterocycles containing Sulfur atom have also been synthesized including fused polycycles, spirocycles, axially chiral motifs etc. by advent of using chiral organocatalysts. Both covalent and non‐covalent activation have been explored by different organocatalysts to execute multistep cascade processes for facile access of interesting molecular architectures containing Sulfur atom. Present review documents the different avenues of organocatalysis for the asymmetric synthesis of thiacycles from 2010 onward. The article has been segmented by the nature of organocatalyst used and special attention has been put on the mechanistic rationale of the process to understand the stereochemical output.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e70218"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753802","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite acetylation being the go‐to protecting group for alcohols, regulatory restrictions on the use of acetic anhydride as the acetylating agent has forced to look for other alternatives. Recently, ethyl acetate and vinyl acetate have found applications as acetyl surrogate for protection of alcohols, but the reported methods are a few. Given the recent emphasis on development of green and sustainable methodology, here, we present one of the most efficient, user friendly, and environmentally benign methods for acetylation of alcohols via irreversible trans‐esterification of alcohols with vinyl acetate under sonication in the presence of a catalytic amount of anhydrous potassium carbonate as reusable heterogeneous catalyst. The reaction gives quantitative yields, uses recyclable vinyl acetate as solvent, needs no work up, and reuses the catalyst up to five times without needing any processing after use. The method demonstrated excellent green matrices as evident from low E‐factor (2.31) and PMI (3.62), and high RME (73.43%) at multigram scale.
{"title":"Potassium Carbonate as a Reusable Heterogeneous Catalyst for Acetylation of Alcohols with Vinyl Acetate Under Sonication: A Sustainable Approach","authors":"Stability Nongrum , Prof.Dr. Ghanashyam Bez","doi":"10.1002/ajoc.202500594","DOIUrl":"10.1002/ajoc.202500594","url":null,"abstract":"<div><div>Despite acetylation being the go‐to protecting group for alcohols, regulatory restrictions on the use of acetic anhydride as the acetylating agent has forced to look for other alternatives. Recently, ethyl acetate and vinyl acetate have found applications as acetyl surrogate for protection of alcohols, but the reported methods are a few. Given the recent emphasis on development of green and sustainable methodology, here, we present one of the most efficient, user friendly, and environmentally benign methods for acetylation of alcohols via irreversible trans‐esterification of alcohols with vinyl acetate under sonication in the presence of a catalytic amount of anhydrous potassium carbonate as reusable heterogeneous catalyst. The reaction gives quantitative yields, uses recyclable vinyl acetate as solvent, needs no work up, and reuses the catalyst up to five times without needing any processing after use. The method demonstrated excellent green matrices as evident from low <em>E</em>‐factor (2.31) and PMI (3.62), and high RME (73.43%) at multigram scale.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e00594"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753804","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study introduces a novel Schiff base ligand (L) and its metal complexes (L‐Cu2+, L‐Ni2+, and L‐Zn2+), which exhibit remarkable antifungal and antibacterial activity against the plant pathogens Alternaria solani and Xanthomonas euvesicatoria, the causative agents of early blight and bacterial spot in tomatoes, respectively. At 250 µg/mL, all compounds demonstrated exceptional antimicrobial activity, achieving 100% inhibition of A. solani, surpassing the commercial fungicide's 91% inhibition. Additionally, the compounds produced substantial inhibition zones against X. euvesicatoria. They also showed scavenging of reactive oxygen species (ROS), indicating their potential to mitigate oxidative stress in plant cells. Phytotoxicity tests at 300 µg/mL confirmed that none of the compounds adversely affected tomato seed germination. The dual action of pathogen inhibition and ROS neutralization, combined with non‐toxicity to plants, suggests that L and its complexes are promising candidates for crop protection. Across all assays, efficacy was ranked as L‐Cu2+ > L > L‐Zn2+ ≈ L‐Ni2+, with the L‐Cu2+ complex demonstrating superior overall performance.
本研究介绍了一种新的希夫碱配体(L)及其金属配合物（L‐Cu2+、L‐Ni2+和L‐Zn2+），它们对番茄早疫病和细菌性斑疹的病原菌茄疫病菌（Alternaria solani）和euvesicatoria黄单胞菌（Xanthomonas euvesicatoria）具有显著的抗真菌和抗菌活性。在250µg/mL浓度下，所有化合物均表现出优异的抑菌活性，对茄蚜的抑菌率达到100%，超过了商用杀菌剂91%的抑菌率。此外，这些化合物还能产生大量的抑菌带。它们还显示出清除活性氧（ROS）的能力，表明它们有可能减轻植物细胞中的氧化应激。300µg/mL的植物毒性试验证实，这些化合物都没有对番茄种子萌发产生不利影响。L及其复合物具有抑制病原菌和中和活性氧的双重作用，且对植物无毒，这表明L及其复合物具有很好的作物保护潜力。在所有测试中，功效等级为L‐Cu2+ >； L > L‐Zn2+≈L‐Ni2+，其中L‐Cu2+复合物表现出优越的整体性能。
{"title":"Antimicrobial Potential of a Quinoline‐Based Novel Schiff Base Against Tomato Crop Pathogens","authors":"Siddharth Gautam , Khyati Tomar , Sadhna Chauhan , Anjana Sarkar , Md. Najbul Hoque , Nancy Gupta","doi":"10.1002/ajoc.202500476","DOIUrl":"10.1002/ajoc.202500476","url":null,"abstract":"<div><div>This study introduces a novel Schiff base ligand (<strong>L</strong>) and its metal complexes (L‐Cu<sup>2+</sup>, L‐Ni<sup>2+</sup>, and L‐Zn<sup>2+</sup>), which exhibit remarkable antifungal and antibacterial activity against the plant pathogens <em>Alternaria solani</em> and <em>Xanthomonas euvesicatoria</em>, the causative agents of early blight and bacterial spot in tomatoes, respectively. At 250 µg/mL, all compounds demonstrated exceptional antimicrobial activity, achieving 100% inhibition of <em>A. solani</em>, surpassing the commercial fungicide's 91% inhibition. Additionally, the compounds produced substantial inhibition zones against <em>X. euvesicatoria</em>. They also showed scavenging of reactive oxygen species (ROS), indicating their potential to mitigate oxidative stress in plant cells. Phytotoxicity tests at 300 µg/mL confirmed that none of the compounds adversely affected tomato seed germination. The dual action of pathogen inhibition and ROS neutralization, combined with non‐toxicity to plants, suggests that <strong>L</strong> and its complexes are promising candidates for crop protection. Across all assays, efficacy was ranked as L‐Cu<sup>2+</sup> > L > L‐Zn<sup>2+</sup> ≈ L‐Ni<sup>2+</sup>, with the L‐Cu<sup>2+</sup> complex demonstrating superior overall performance.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e00476"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A general means to access segmentally deuterium‐labeled alkyl chains for applications in mass spectrometry, neutron scattering, and related biochemical studies is reported, using a key nickel boride mediated reductive desulfurization of substituted thiophenes. This approach enabled the preparation of (3,3,4,4,5,5,6,6‐2H8)undecanoic acid and 1‐amino(1,1,2,2,3,3,4,4‐2H8)nonane, using only recrystallization or distillation for purification. Both compounds featured segments of four deuterated carbon atoms with > 98.5% overall deuterium incorporation. To assess site‐specific deuterium retention during desulfurization, we demonstrated the utility of molecular rotational resonance (MRR) spectroscopy, which revealed the degree, position, and magnitude of isotope scrambling in a key thiophene reductive desulfurization step and established the methods set forth herein as being suitable for the construction of mass spectrometric standards and applicable to the synthesis of any CH3(CH2)a(CD2)b(CH2)cCOOH (3 ≤ a ≤ 13, 3 ≤ b ≤ 6, c ≥ 1) using only commercially‐available materials. Our studies revealed extensive exchange of the hydrogen atoms on the thiophene carbons during saturation of the ring, ruling out an idealized schema of the reaction that is present in the literature. We further observed reagent‐dependent levels of isotopic scrambling at the benzylic position during desulfurization, challenging the assumption of benzylic stereospecificity in nickel‐mediated reductive desulfurization while affirming the reaction's applicability for segmental deuterium labeling.
{"title":"Segmental Deuterium Labeling of Alkyl Chains by Nickel–Mediated Desulfurization","authors":"Carl Recsei , Reilly E. Sonstrom , Tamim Darwish","doi":"10.1002/ajoc.202500520","DOIUrl":"10.1002/ajoc.202500520","url":null,"abstract":"<div><div>A general means to access segmentally deuterium‐labeled alkyl chains for applications in mass spectrometry, neutron scattering, and related biochemical studies is reported, using a key nickel boride mediated reductive desulfurization of substituted thiophenes. This approach enabled the preparation of (3,3,4,4,5,5,6,6‐<sup>2</sup>H<sub>8</sub>)undecanoic acid and 1‐amino(1,1,2,2,3,3,4,4‐<sup>2</sup>H<sub>8</sub>)nonane, using only recrystallization or distillation for purification. Both compounds featured segments of four deuterated carbon atoms with > 98.5% overall deuterium incorporation. To assess site‐specific deuterium retention during desulfurization, we demonstrated the utility of molecular rotational resonance (MRR) spectroscopy, which revealed the degree, position, and magnitude of isotope scrambling in a key thiophene reductive desulfurization step and established the methods set forth herein as being suitable for the construction of mass spectrometric standards and applicable to the synthesis of any CH<sub>3</sub>(CH<sub>2</sub>)<sub><em>a</em></sub>(CD<sub>2</sub>)<sub><em>b</em></sub>(CH<sub>2</sub>)<sub><em>c</em></sub>COOH (3 ≤ <em>a</em> ≤ 13, 3 ≤ <em>b</em> ≤ 6, <em>c</em> ≥ 1) using only commercially‐available materials. Our studies revealed extensive exchange of the hydrogen atoms on the thiophene carbons during saturation of the ring, ruling out an idealized schema of the reaction that is present in the literature. We further observed reagent‐dependent levels of isotopic scrambling at the benzylic position during desulfurization, challenging the assumption of benzylic stereospecificity in nickel‐mediated reductive desulfurization while affirming the reaction's applicability for segmental deuterium labeling.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e00520"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Thiago Anjos , Mateus W. Rambo , Prof. Damiano Tanini , Prof. Dr. Alan Diego C. Santos , Prof. Ricardo F. Schumacher , Prof. Filipe Penteado
Herein, we present a comprehensive review of recent synthetic strategies for the construction of chalcogen‐decorated compounds (since 2016), focusing on the generation of chalcogen‐based electrophilic or radical species through the use of N─F reagents as oxidants. Several chalcogen compounds have been employed as sources, including chalcogenides, diorganyl dichalcogenides, chalcogenols, chalcogenocyanides, and silver trifluoromethanethiolate. Remarkable advances in the preparation of heterocycles, carbocycles, and acyclic molecules containing chalcogens have been thoroughly discussed. Additionally, this review aims to emphasize mechanistic insights from selected studies and to highlight the potential application of these strategies in building molecular complexity. Finally, we hope to inspire future readers to explore new reactivities and possibilities for the development of novel synthetic strategies under mild and sustainable conditions.
{"title":"Applications of N─F─Based Reagents in the Synthesis of Organochalcogen Compounds","authors":"Thiago Anjos , Mateus W. Rambo , Prof. Damiano Tanini , Prof. Dr. Alan Diego C. Santos , Prof. Ricardo F. Schumacher , Prof. Filipe Penteado","doi":"10.1002/ajoc.202500605","DOIUrl":"10.1002/ajoc.202500605","url":null,"abstract":"<div><div>Herein, we present a comprehensive review of recent synthetic strategies for the construction of chalcogen‐decorated compounds (since 2016), focusing on the generation of chalcogen‐based electrophilic or radical species through the use of N─F reagents as oxidants. Several chalcogen compounds have been employed as sources, including chalcogenides, diorganyl dichalcogenides, chalcogenols, chalcogenocyanides, and silver trifluoromethanethiolate. Remarkable advances in the preparation of heterocycles, carbocycles, and acyclic molecules containing chalcogens have been thoroughly discussed. Additionally, this review aims to emphasize mechanistic insights from selected studies and to highlight the potential application of these strategies in building molecular complexity. Finally, we hope to inspire future readers to explore new reactivities and possibilities for the development of novel synthetic strategies under mild and sustainable conditions.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"14 12","pages":"Article e00605"},"PeriodicalIF":2.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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