Amit Kumar Sharma, Poulami Mandal, Ranjan Mali, Noimur Rahman, Nilay Kumar Pal, Manas K. Ghorai
We present a practical, efficient and highly enantioselective synthetic route to 4,5-dihydropyrrole derivatives via Dynamic Kinetic Resolution (DKR) assisted domino ring opening cyclization (DROC) of racemic aziridines with N,N-dimethyl enaminones employing Cu(I)-(S)-XylBINAP as the catalyst system. The strategy works successfully with various substrates having wider substitution patterns producing a library of 4,5-dihydropyrroles with excellent yields (up to 96%) and excellent enantiomeric excess (ee up to 97%). The application of DKR concept in DROC of aziridines is reported for the first time.
{"title":"Asymmetric Synthesis of 4,5-Dihydropyrrole Derivatives via DKR: DROC of Activated Aziridines with Enaminones","authors":"Amit Kumar Sharma, Poulami Mandal, Ranjan Mali, Noimur Rahman, Nilay Kumar Pal, Manas K. Ghorai","doi":"10.1039/d5qo01590a","DOIUrl":"https://doi.org/10.1039/d5qo01590a","url":null,"abstract":"We present a practical, efficient and highly enantioselective synthetic route to 4,5-dihydropyrrole derivatives via Dynamic Kinetic Resolution (DKR) assisted domino ring opening cyclization (DROC) of racemic aziridines with <em>N,N</em>-dimethyl enaminones employing Cu(I)-(<em>S</em>)-XylBINAP as the catalyst system. The strategy works successfully with various substrates having wider substitution patterns producing a library of 4,5-dihydropyrroles with excellent yields (up to 96%) and excellent enantiomeric excess (<em>ee</em> up to 97%). The application of DKR concept in DROC of aziridines is reported for the first time.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"130 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908136","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}
We report a unified strategy utilizing bench stable hypervalent iodine(III) reagent in the construction of phenanthridine, isoquinoline, quinoline and pyridine from aryl/alkenyl imidates. Mechanistic studies revealed the involvement of imidate radical intermediates, which undergoes intramolecular homolytic aromatic substitution (HAS) to give range of heteroarenes. The reaction can also be extended to the gram scale synthesis and exhibits high functional group tolerance to offers an efficient alternative for the construction of N-containing arenes.
{"title":"A Unified Strategy to access N-Heterocycles Enabled by Hypervalent Iodine(III) Reagent Mediated Imidate Radical Cyclization","authors":"Akshay S. Pathare, Sermadurai Selvakumar","doi":"10.1039/d5qo01301a","DOIUrl":"https://doi.org/10.1039/d5qo01301a","url":null,"abstract":"We report a unified strategy utilizing bench stable hypervalent iodine(III) reagent in the construction of phenanthridine, isoquinoline, quinoline and pyridine from aryl/alkenyl imidates. Mechanistic studies revealed the involvement of imidate radical intermediates, which undergoes intramolecular homolytic aromatic substitution (HAS) to give range of heteroarenes. The reaction can also be extended to the gram scale synthesis and exhibits high functional group tolerance to offers an efficient alternative for the construction of N-containing arenes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908141","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}
Yunfei Du, Dan Xiao, Jiaxin He, Kaiyue Yang, Zhijian Wang, Cong Li
The development of efficient synthetic approaches to α-ketoamides remains a significant objective. Herein, we report a mild and met-al-free method for the preparation of α-ketoamides from glyoxylic acids, mediated by a dimethylaminoiodine(III)/PPh3 system. Mechanistic studies suggest that the transformation proceeds through an ionic pathway, involving the formation of an active dimethylamino-phosphonium species derived from the reaction between the novel dimethylamino-iodine(III) reagent (DMI) and PPh3.2
{"title":"Dimethylamino-Iodine(III)/PPh3 -Mediated Synthesis of α-Ketoamides from Glyoxylic Acids","authors":"Yunfei Du, Dan Xiao, Jiaxin He, Kaiyue Yang, Zhijian Wang, Cong Li","doi":"10.1039/d5qo01675d","DOIUrl":"https://doi.org/10.1039/d5qo01675d","url":null,"abstract":"The development of efficient synthetic approaches to α-ketoamides remains a significant objective. Herein, we report a mild and met-al-free method for the preparation of α-ketoamides from glyoxylic acids, mediated by a dimethylaminoiodine(III)/PPh3 system. Mechanistic studies suggest that the transformation proceeds through an ionic pathway, involving the formation of an active dimethylamino-phosphonium species derived from the reaction between the novel dimethylamino-iodine(III) reagent (DMI) and PPh3.2","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903683","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}
Fused pyran motifs are key structural components in many bioactive compounds and pharmaceutical drugs. Traditional methods for synthesizing these heterocycles, such as Fe-catalyzed annulation and photocatalytic approaches, often face challenges including the use of precious metals, long reaction times, and reliance on solvents. Here, we introduce a mechanochemical, piezoelectric-catalyzed decarboxylative cascade cyclization of 1,7-enynes and α-keto acids using BaTiO₃ as a catalyst under ball milling conditions. This method provides several advantages, including solvent-free conditions, significantly reduced reaction times (12 minutes), and no need for transition-metal catalysts or external photosensitizers. Additionally, the piezocatalyst demonstrates recyclability over multiple cycles with minimal loss in yield. Our approach offers a sustainable and efficient alternative to traditional catalytic systems, providing a versatile strategy for the synthesis of fused pyran derivatives.
{"title":"Piezocatalyzed Cascade Cyclization of 1,7-Enynes with α-Keto Acids under Ball Milling","authors":"Yashuang Liu, Heng Li, Yan Liu, Bingxin Yuan","doi":"10.1039/d5qo01278c","DOIUrl":"https://doi.org/10.1039/d5qo01278c","url":null,"abstract":"Fused pyran motifs are key structural components in many bioactive compounds and pharmaceutical drugs. Traditional methods for synthesizing these heterocycles, such as Fe-catalyzed annulation and photocatalytic approaches, often face challenges including the use of precious metals, long reaction times, and reliance on solvents. Here, we introduce a mechanochemical, piezoelectric-catalyzed decarboxylative cascade cyclization of 1,7-enynes and α-keto acids using BaTiO₃ as a catalyst under ball milling conditions. This method provides several advantages, including solvent-free conditions, significantly reduced reaction times (12 minutes), and no need for transition-metal catalysts or external photosensitizers. Additionally, the piezocatalyst demonstrates recyclability over multiple cycles with minimal loss in yield. Our approach offers a sustainable and efficient alternative to traditional catalytic systems, providing a versatile strategy for the synthesis of fused pyran derivatives.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145897772","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}
Mohammad Sadeq Mousavi, Antonio Massa, Mario Waser
Base-mediated reactions between hydroxy-pyrones or isochroman-3,4-diones and allenoates or butynoates allow for the direct synthesis of various 1,2,3-substituted phenols and naphthols under mild conditions. These transformations are supposed to proceed via a [4+2]-cycloaddition of the starting materials first, followed by an immediate decarboxylation/re-aromatization process.
{"title":"Syntheses of 1,2,3-functionalized naphthols and phenols by decarboxylative cycloaddition/aromatization reactions of a-oxygenated lactones with allenoates or electron-deficient alkynes.","authors":"Mohammad Sadeq Mousavi, Antonio Massa, Mario Waser","doi":"10.1039/d5qo01582k","DOIUrl":"https://doi.org/10.1039/d5qo01582k","url":null,"abstract":"Base-mediated reactions between hydroxy-pyrones or isochroman-3,4-diones and allenoates or butynoates allow for the direct synthesis of various 1,2,3-substituted phenols and naphthols under mild conditions. These transformations are supposed to proceed via a [4+2]-cycloaddition of the starting materials first, followed by an immediate decarboxylation/re-aromatization process.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145897773","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}
Yingmin Ji, Roser Pleixats, Israel Fernandez, Carolina Gimbert-Suriñach, Adelina Vallribera, Albert Granados
We report a novel EDA complex stabilized by π-π and CH-π interactions between thianthrene-derived radical precursors and unsaturated carboxylic acids or alcohols. This photocatalyst-free strategy allows access to different disubstituted heterocycles. This transformation proceeds efficiently under visible-light irradiation, delivering a broad array of structurally diverse lactones and tetrahydrofuranes in good to excellent yields. Both aryl and alkyl-derived thianthrenium salts are competent substrates, including primary, secondary, and sterically hindered tertiary alkyl derivatives. In addition, this work shows the first example of iminothianthrenes participating in EDA-complex driven photochemistry providing access to aminated tetrahydrofuranes. UV-Vis spectroscopy, NMR analysis and DFT calculations support the formation of the groundstate EDA complex stabilized by π-π and CH-π interactions. The reaction proceeds via a non-chain pathway as indicated by the photochemical quantum yield.
{"title":"EDA-complex photoactivation of thianthrene-based radical precursors enables divergent access to functionalized saturated heterocycles","authors":"Yingmin Ji, Roser Pleixats, Israel Fernandez, Carolina Gimbert-Suriñach, Adelina Vallribera, Albert Granados","doi":"10.1039/d5qo01397f","DOIUrl":"https://doi.org/10.1039/d5qo01397f","url":null,"abstract":"We report a novel EDA complex stabilized by π-π and CH-π interactions between thianthrene-derived radical precursors and unsaturated carboxylic acids or alcohols. This photocatalyst-free strategy allows access to different disubstituted heterocycles. This transformation proceeds efficiently under visible-light irradiation, delivering a broad array of structurally diverse lactones and tetrahydrofuranes in good to excellent yields. Both aryl and alkyl-derived thianthrenium salts are competent substrates, including primary, secondary, and sterically hindered tertiary alkyl derivatives. In addition, this work shows the first example of iminothianthrenes participating in EDA-complex driven photochemistry providing access to aminated tetrahydrofuranes. UV-Vis spectroscopy, NMR analysis and DFT calculations support the formation of the groundstate EDA complex stabilized by π-π and CH-π interactions. The reaction proceeds via a non-chain pathway as indicated by the photochemical quantum yield.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895220","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}
Kendra Kumar Shrestha, Olutayo Nathanael Farinde, Abigail Gohmann, Radha Kondapalli, Oreoluwa Adeyemo, Satheesh Vanaparthi, Justin Maxwell, Vinod G. Landge, Allison Gottshall, G. Brant Hunt, Michael Christopher Young
The regioselectivity for insertion reactions of allylamines is almost exclusively biased towards γ-functionalization for internal alkenes. To expand the synthetic toolbox to access unique new allylamine structures, we've demonstrated how controlling the surface charge of in situ-generated Pd nanoparticle catalysts can be exploited to achieve highly selective β-functionalization of internal allylamine substrates. A key to the regioselectivity switch is the decreased activation of the olefin by the less charged catalyst, allowing substrate electronic contributions to help dictate the product regiochemistry.
{"title":"β-Selective Heck Reactions of Unprotected Allylamines Driven by Surface Charge of in situ-Formed Pd Nanoparticles","authors":"Kendra Kumar Shrestha, Olutayo Nathanael Farinde, Abigail Gohmann, Radha Kondapalli, Oreoluwa Adeyemo, Satheesh Vanaparthi, Justin Maxwell, Vinod G. Landge, Allison Gottshall, G. Brant Hunt, Michael Christopher Young","doi":"10.1039/d5qo01463h","DOIUrl":"https://doi.org/10.1039/d5qo01463h","url":null,"abstract":"The regioselectivity for insertion reactions of allylamines is almost exclusively biased towards γ-functionalization for internal alkenes. To expand the synthetic toolbox to access unique new allylamine structures, we've demonstrated how controlling the surface charge of in situ-generated Pd nanoparticle catalysts can be exploited to achieve highly selective β-functionalization of internal allylamine substrates. A key to the regioselectivity switch is the decreased activation of the olefin by the less charged catalyst, allowing substrate electronic contributions to help dictate the product regiochemistry.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895504","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}
An efficient synthesis of fused cinnolines has been developed viaRh(III)-catalysed [4+2] annulation of N-aryl pyrazolones with iodonium ylides. Fused cinnolines were provided in up to 81 yields for 27 examples. This protocol features with the gram-scale scalability. Notably, the titled targets exhibit strong fluorescence, which enables potential application in fluorescent probe.
{"title":"Rh(III)-Catalysed [4+2] Annulation of N-Arylpyrazolones with Iodonium Ylides: Access to Fused Cinnolines","authors":"Xiaoting Chen, Chaoyu Wang, Xiujuan Zheng, Yadong Feng, Junjie Ma, Xiuling Cui","doi":"10.1039/d5qo01414j","DOIUrl":"https://doi.org/10.1039/d5qo01414j","url":null,"abstract":"An efficient synthesis of fused cinnolines has been developed viaRh(III)-catalysed [4+2] annulation of N-aryl pyrazolones with iodonium ylides. Fused cinnolines were provided in up to 81 yields for 27 examples. This protocol features with the gram-scale scalability. Notably, the titled targets exhibit strong fluorescence, which enables potential application in fluorescent probe.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895742","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}
Ming-Yu Chen, Pierre-Adrien Payard, Marie-Eve L. Perrin, Julien Vantourout
The direct construction of high-value pyridine scaffolds through manganese-catalyzed alkene dicarbofunctionalization starting from ubiquitous carbonyls and heterocyclic compounds is reported. This protocol provides an efficient platform for constructing a wide array of γ-heterocyclic ketone derivatives, which are useful bioactive scaffolds, with high atom economy and controlled regioselectivity. An intramolecular approach was also developed to efficiently synthesize α-tetralones, tetrahydroquinolines, and benz[h]isoquinolines which have garnered significant attention due to their potential applications in medicinal chemistry but also in materials science. In addition, a complementary electrochemical protocol has also been developed to avoid the use of stoichiometric amounts of Mn(III)-salts. Finally, several control experiments allowed for a proposed mechanism to be assembled thus rationalizing the crucial role of N-methoxypyridinium salts.
{"title":"Direct Construction of High-Value Pyridine Scaffolds through Manganese-Promoted Alkene Dicarbofunctionalization","authors":"Ming-Yu Chen, Pierre-Adrien Payard, Marie-Eve L. Perrin, Julien Vantourout","doi":"10.1039/d5qo01424g","DOIUrl":"https://doi.org/10.1039/d5qo01424g","url":null,"abstract":"The direct construction of high-value pyridine scaffolds through manganese-catalyzed alkene dicarbofunctionalization starting from ubiquitous carbonyls and heterocyclic compounds is reported. This protocol provides an efficient platform for constructing a wide array of γ-heterocyclic ketone derivatives, which are useful bioactive scaffolds, with high atom economy and controlled regioselectivity. An intramolecular approach was also developed to efficiently synthesize α-tetralones, tetrahydroquinolines, and benz[h]isoquinolines which have garnered significant attention due to their potential applications in medicinal chemistry but also in materials science. In addition, a complementary electrochemical protocol has also been developed to avoid the use of stoichiometric amounts of Mn(III)-salts. Finally, several control experiments allowed for a proposed mechanism to be assembled thus rationalizing the crucial role of <em>N</em>-methoxypyridinium salts.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895149","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}
Zhuo Chen, Hui-Qiang Li, Shun-Bin Xu, Ling-Rui Zhou, Tongling Qin, Wenxia Hu, Tao Li, Ruo-Yi Hou, Zi-Yu Lin, E Tang
An efficient palladium-catalysed aminocarbonylation reaction between aryl thianthrenium salts and amines, using Mo(CO)₆ as a solid CO surrogate, has been developed. A wide range of aliphatic and aryl carboxamides, including secondary and tertiary amides, as well as N-aliphatic-linear amides, N-aliphatic-cyclic amides, and N-aryl amides, and some carboxamide derivatives of bioactive molecules such as loratadine, fenofibrate, and cloquintocet-mexyl, have been synthesized under safe and mild conditions and with good to excellent yields and with broad functional group tolerance, including the bromo and iodo groups, offering a new avenue for the production of aryl carboxamides with potential applications.
{"title":"Palladium-catalysed aminocarbonylation of aryl thianthrenium salts to aryl carboxamides using Mo(CO)₆ as a CO source","authors":"Zhuo Chen, Hui-Qiang Li, Shun-Bin Xu, Ling-Rui Zhou, Tongling Qin, Wenxia Hu, Tao Li, Ruo-Yi Hou, Zi-Yu Lin, E Tang","doi":"10.1039/d5qo01508a","DOIUrl":"https://doi.org/10.1039/d5qo01508a","url":null,"abstract":"An efficient palladium-catalysed aminocarbonylation reaction between aryl thianthrenium salts and amines, using Mo(CO)₆ as a solid CO surrogate, has been developed. A wide range of aliphatic and aryl carboxamides, including secondary and tertiary amides, as well as N-aliphatic-linear amides, N-aliphatic-cyclic amides, and N-aryl amides, and some carboxamide derivatives of bioactive molecules such as loratadine, fenofibrate, and cloquintocet-mexyl, have been synthesized under safe and mild conditions and with good to excellent yields and with broad functional group tolerance, including the bromo and iodo groups, offering a new avenue for the production of aryl carboxamides with potential applications.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895150","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}
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