Krisztián Bíró, Miklós Nyerges, Imre Pápai, Dániel Csókás
Highly efficient one‐pot synthesis of a series of indeno[2,1‐b]quinolin‐6‐ones 10 and indolo[1,2‐b]isoquinoline‐6,12‐diones 12 is portrayed from easily accessible starting materials such as indan‐1‐ones 7 and 2‐nitrobenzaldehydes 9. The reaction mechanism studies by control experiments and computational analysis reveal that the reactions are initiated by attack of a conjugate base of indanones 7 to the aldehyde group or the adjacent nitro group of 2‐nitrobenzaldehydes 9 followed by intramolecular cyclization involving a second anion to furnish the appropriate products. The heterocyclic compounds were obtained in moderate to good yields.
{"title":"Intermolecular Carbanion Attack on Nitro vs. Carbonyl Group: Experimental and Computational Studies","authors":"Krisztián Bíró, Miklós Nyerges, Imre Pápai, Dániel Csókás","doi":"10.1002/ejoc.202400612","DOIUrl":"https://doi.org/10.1002/ejoc.202400612","url":null,"abstract":"Highly efficient one‐pot synthesis of a series of indeno[2,1‐b]quinolin‐6‐ones 10 and indolo[1,2‐b]isoquinoline‐6,12‐diones 12 is portrayed from easily accessible starting materials such as indan‐1‐ones 7 and 2‐nitrobenzaldehydes 9. The reaction mechanism studies by control experiments and computational analysis reveal that the reactions are initiated by attack of a conjugate base of indanones 7 to the aldehyde group or the adjacent nitro group of 2‐nitrobenzaldehydes 9 followed by intramolecular cyclization involving a second anion to furnish the appropriate products. The heterocyclic compounds were obtained in moderate to good yields.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142596838","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}
Yoonji Heo, Minseo Ji, Chae Young Ryu, Haein Kim, Isaac Choi, Sung Min Kang, Min Kim
Polydopamine (PDA) is a synthetic material synthesized through the oxidative self‐polymerization of dopamine under alkaline conditions. This material emulates the adhesive properties of mussel foot proteins, allowing the formation of robust and stable organic coatings on various surfaces. Researchers have attempted to identify and improve the surface‐coating properties of PDA by incorporating additional organic functional groups. This review explores the structural modifications of dopamine molecules at the organic chemistry level, with a focus on changes in the catechol moiety and aliphatic amines, and examines their impact on the applications of PDA. The flexibility of these modifications underscores their importance for optimizing PDA coatings for a wide range of applications.
{"title":"Structural Modifications on Dopamine Molecules toward Polydopamine Applications","authors":"Yoonji Heo, Minseo Ji, Chae Young Ryu, Haein Kim, Isaac Choi, Sung Min Kang, Min Kim","doi":"10.1002/ejoc.202401035","DOIUrl":"https://doi.org/10.1002/ejoc.202401035","url":null,"abstract":"Polydopamine (PDA) is a synthetic material synthesized through the oxidative self‐polymerization of dopamine under alkaline conditions. This material emulates the adhesive properties of mussel foot proteins, allowing the formation of robust and stable organic coatings on various surfaces. Researchers have attempted to identify and improve the surface‐coating properties of PDA by incorporating additional organic functional groups. This review explores the structural modifications of dopamine molecules at the organic chemistry level, with a focus on changes in the catechol moiety and aliphatic amines, and examines their impact on the applications of PDA. The flexibility of these modifications underscores their importance for optimizing PDA coatings for a wide range of applications.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594927","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}
Alexander Nikolaevich Larin, Elena Kimovna Avakyan, Oleg Demidov, Anastasia Alekseevna Borovleva, Alexander A. Zubenko, Diana Yu. Pobedinskaya, Artem Pavlovich Ermolenko, Stepan E. Kolosov, Ivan V. Borovlev
A novel and efficient method for the synthesis of 2-alkylamino and 2-dialkylamino derivatives of N-oxides of 5-, 6-, 7- and 8-nitroquinolines, which can potentially exhibit biological activity, as containing a pharmacophoric quinoline fragment, is described herein. The reactions of 5(6,7,8)-nitroquinoline N-oxides with various primary or secondary amines in the presence of potassium ferricyanide at in aqueous dioxane medium afforded the corresponding secondary and tertiary amines in moderate to excellent yields. This reaction is the first example of a Chichibabin reaction leading to the formation of 2-alkylaminoquinoline derivatives at position 2 under mild conditions. A study of the antibacterial activity of some products was carried out.
{"title":"An Oxidative SNH Alkylamination of 5(6,7,8)-Nitroquinoline N-Oxides in Aqueous Dioxane Medium","authors":"Alexander Nikolaevich Larin, Elena Kimovna Avakyan, Oleg Demidov, Anastasia Alekseevna Borovleva, Alexander A. Zubenko, Diana Yu. Pobedinskaya, Artem Pavlovich Ermolenko, Stepan E. Kolosov, Ivan V. Borovlev","doi":"10.1002/ejoc.202401060","DOIUrl":"https://doi.org/10.1002/ejoc.202401060","url":null,"abstract":"A novel and efficient method for the synthesis of 2-alkylamino and 2-dialkylamino derivatives of N-oxides of 5-, 6-, 7- and 8-nitroquinolines, which can potentially exhibit biological activity, as containing a pharmacophoric quinoline fragment, is described herein. The reactions of 5(6,7,8)-nitroquinoline N-oxides with various primary or secondary amines in the presence of potassium ferricyanide at in aqueous dioxane medium afforded the corresponding secondary and tertiary amines in moderate to excellent yields. This reaction is the first example of a Chichibabin reaction leading to the formation of 2-alkylaminoquinoline derivatives at position 2 under mild conditions. A study of the antibacterial activity of some products was carried out.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594534","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}
Salome L. Heim, Almudena Gallego, Valeria Bertozzi, Sebastiaan van der Poel, Luca Ornago, Alessandro Prescimone, Herre S. J. van der Zant, Marcel Mayor
To investigate interference phenomena and conductance properties in mechanically controlled break junctions (MCBJs), macrocycles 1 and 2 (BMCs: for BenzeneMacroCycles), containing a meta-substituted benzene moiety with solubilizing tert-butyl groups, as well as structures 3 and 4 (TMCs: for ThiopheneMacroCycles), featuring 2,5-connected 3,4-hexyl-thiophene corners, were synthesized. Macrocycles 1 and 2 respectively 3 and 4 differ in the positions of the acetyl-protected sulfur anchoring groups, which impacts both, the individual transport efficiency of their parallel electronic pathways and their overall molecular wire lengths. All macrocycles were synthesized based on a series of Sonogashira cross-coupling reactions. For 3 and 4, a 2-(4-pyridinyl)ethyl protecting group for the sulfur atoms was successful, while for macrocycles 1 and 2 the more common tert-butyl protecting group did the job. To our delight, proof-of-concept charge transport studies conducted in an MCBJ setup demonstrated the expected trends regarding improved conductance intensities for the TMCs compared to the BMCs. Furthermore, the corresponding molecular plateaus from the breaking experiments were in the expected length range of the S-S distances for all compounds. We also found that the overall conductance seems to follow a more complex transport mechanism than just the sum of contributions from both channels.
{"title":"Design and Synthesis of Multipath Compact Cyclophanes for Quantum Interference Studies","authors":"Salome L. Heim, Almudena Gallego, Valeria Bertozzi, Sebastiaan van der Poel, Luca Ornago, Alessandro Prescimone, Herre S. J. van der Zant, Marcel Mayor","doi":"10.1002/ejoc.202400914","DOIUrl":"https://doi.org/10.1002/ejoc.202400914","url":null,"abstract":"To investigate interference phenomena and conductance properties in mechanically controlled break junctions (MCBJs), macrocycles 1 and 2 (BMCs: for BenzeneMacroCycles), containing a meta-substituted benzene moiety with solubilizing tert-butyl groups, as well as structures 3 and 4 (TMCs: for ThiopheneMacroCycles), featuring 2,5-connected 3,4-hexyl-thiophene corners, were synthesized. Macrocycles 1 and 2 respectively 3 and 4 differ in the positions of the acetyl-protected sulfur anchoring groups, which impacts both, the individual transport efficiency of their parallel electronic pathways and their overall molecular wire lengths. All macrocycles were synthesized based on a series of Sonogashira cross-coupling reactions. For 3 and 4, a 2-(4-pyridinyl)ethyl protecting group for the sulfur atoms was successful, while for macrocycles 1 and 2 the more common tert-butyl protecting group did the job. To our delight, proof-of-concept charge transport studies conducted in an MCBJ setup demonstrated the expected trends regarding improved conductance intensities for the TMCs compared to the BMCs. Furthermore, the corresponding molecular plateaus from the breaking experiments were in the expected length range of the S-S distances for all compounds. We also found that the overall conductance seems to follow a more complex transport mechanism than just the sum of contributions from both channels.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588980","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}
Victoria Magrioti, Evanthia Papadaki, Antonia Kapoti, Roza Leitourgaki, Aikaterini Vogiatzi
N-Heterocyclic carbenes (NHCs) generated from imidazolium, imidazopyridinium and imidazoquinolinium hydrochlorides in situ using base and microwave irradiation were employed as organocatalysts to yield homoenolates from cinnamaldehyde and its aryl-substituted analogs. Depending on the catalytic base either γ-lactones were prepared when the strong base tBuOK was used or the corresponding saturated ethyl 3-aryl propionates were synthesized with the milder DIPEA base. Novel imidazopyridinium and imidazoquinolinium hydrochlorides were synthesized and were compared to commercially available NHCs IMes and IDip for their catalytic activity. The optimum reaction conditions were established using IMes and the broad scope of both reactions was investigated using the 4 most efficient NHCs.
{"title":"NHC-Catalyzed, Microwave-Assisted and Base-Dependent Reactions of Substituted Cinnamaldehydes Towards γ-Lactones or Saturated Esters","authors":"Victoria Magrioti, Evanthia Papadaki, Antonia Kapoti, Roza Leitourgaki, Aikaterini Vogiatzi","doi":"10.1002/ejoc.202401047","DOIUrl":"https://doi.org/10.1002/ejoc.202401047","url":null,"abstract":"N-Heterocyclic carbenes (NHCs) generated from imidazolium, imidazopyridinium and imidazoquinolinium hydrochlorides in situ using base and microwave irradiation were employed as organocatalysts to yield homoenolates from cinnamaldehyde and its aryl-substituted analogs. Depending on the catalytic base either γ-lactones were prepared when the strong base tBuOK was used or the corresponding saturated ethyl 3-aryl propionates were synthesized with the milder DIPEA base. Novel imidazopyridinium and imidazoquinolinium hydrochlorides were synthesized and were compared to commercially available NHCs IMes and IDip for their catalytic activity. The optimum reaction conditions were established using IMes and the broad scope of both reactions was investigated using the 4 most efficient NHCs.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589215","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}
Jonathan Martins, Abed Bil, José Kovensky, Sylvestre Toumieux, Sylvain Laclef
Deinococcucin A is a secondary metabolite isolated from a gut bacteria of carpenter ant, member of extremophilic Deinoccocus family. The structure is a glycolipid containing N-acetyl glucosamine, linked in α anomeric position to a chiral 2,3-dihydroxypropanamide moiety. We succeeded a new strategy starting directly from N-acetylglucosamine and transforming in an efficient manner an allyl group to the corresponding chiral α-hydroxyamide. Three key steps were used: the oxidation of primary amine to nitrile using TCCA, as well as its hydrolysis to the corresponding amide using palladium (II) catalyzed conditions. The synthesis was completed in only 10 steps with an overall yield of 3%.
{"title":"First Total Synthesis of Deinococcucin A, a Key Glycolipid Found in Cell Membranes of Extremophilic Bacteria.","authors":"Jonathan Martins, Abed Bil, José Kovensky, Sylvestre Toumieux, Sylvain Laclef","doi":"10.1002/ejoc.202400879","DOIUrl":"https://doi.org/10.1002/ejoc.202400879","url":null,"abstract":"Deinococcucin A is a secondary metabolite isolated from a gut bacteria of carpenter ant, member of extremophilic Deinoccocus family. The structure is a glycolipid containing N-acetyl glucosamine, linked in α anomeric position to a chiral 2,3-dihydroxypropanamide moiety. We succeeded a new strategy starting directly from N-acetylglucosamine and transforming in an efficient manner an allyl group to the corresponding chiral α-hydroxyamide. Three key steps were used: the oxidation of primary amine to nitrile using TCCA, as well as its hydrolysis to the corresponding amide using palladium (II) catalyzed conditions. The synthesis was completed in only 10 steps with an overall yield of 3%.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588979","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}
Plastics play a crucial role in the survival and advancement of human civilization. However, the increasing challenge of plastic pollution presents significant obstacles. Disposal methods such as incineration and landfilling result in substantial resource wastage and pose potential environmental hazards. The slow progress in recycling and reusing waste plastics hinders their industrial application and effective response to environmental crises. Photocatalysis offers promising solutions for the future of plastic recycling, particularly with the recent increase in photocatalytic degradation methods for polystyrene (PS). This review provides a comprehensive overview of the latest advancements in the photooxidation of PS into high-value chemicals.
{"title":"Photooxidation of Polystyrene into High-Value Chemicals","authors":"Shusheng Jiang, Yunhan Chen, Yahao Huang, Peng Hu","doi":"10.1002/ejoc.202401109","DOIUrl":"https://doi.org/10.1002/ejoc.202401109","url":null,"abstract":"Plastics play a crucial role in the survival and advancement of human civilization. However, the increasing challenge of plastic pollution presents significant obstacles. Disposal methods such as incineration and landfilling result in substantial resource wastage and pose potential environmental hazards. The slow progress in recycling and reusing waste plastics hinders their industrial application and effective response to environmental crises. Photocatalysis offers promising solutions for the future of plastic recycling, particularly with the recent increase in photocatalytic degradation methods for polystyrene (PS). This review provides a comprehensive overview of the latest advancements in the photooxidation of PS into high-value chemicals.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580272","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 palladium-catalyzed domino radical sulfonylation and alkynylation of simple alkynes has been developed for the rapid construction of privileged scaffolds containing sulfone and 1,3-enyne motifs. The reaction of sulfonyl iodide with simple alkynes proceeded smoothly under mild conditions to afford a variety of sulfone-containing 1,3-enynes in good yields and with excellent selectivities.
{"title":"Palladium-Catalyzed Domino Synthesis of Sulfone-Containing 1,3-Enynes from Simple Alkynes and Sulfonyl Iodides","authors":"Jing Wang, Jianwei Wang, Jun Ying","doi":"10.1002/ejoc.202401028","DOIUrl":"https://doi.org/10.1002/ejoc.202401028","url":null,"abstract":"A palladium-catalyzed domino radical sulfonylation and alkynylation of simple alkynes has been developed for the rapid construction of privileged scaffolds containing sulfone and 1,3-enyne motifs. The reaction of sulfonyl iodide with simple alkynes proceeded smoothly under mild conditions to afford a variety of sulfone-containing 1,3-enynes in good yields and with excellent selectivities.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588981","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 series of phenoxazine embedded heteroporphyrins containing one phenoxazine, two pyrroles and one heterocycle, such as furan, thiophene, selenophene and telluorophene, connected through four meso carbon atoms were synthesized by condensing one equivalent of phenoxazine-based tripyrrane with one equivalent of the appropriate 2,5-bis(hydroxymethyl-p-tolyl) heterocycle under acid-catalyzed conditions, and their structure, spectral and electrochemical properties were compared with those of previously reported phenothiazine embedded heteroporphyrins. The X-ray crystal structure of the phenoxazine embedded selenoporphyrin revealed that the selenophene ring, which is opposite phenoxazine moiety, points outward from the macrocyclic core, and the phenoxazine unit deviated by an angle of 39.47° from the mean plane defined by the four meso carbons atoms. The replacement of the phenothiazine unit in phenothiazine embedded heteroporphyrins with a phenoxazine unit led to significant alteration of the electronic properties of the macrocycles, as reflected in their spectral and electrochemical properties. The absorption spectra of phenoxazine embedded heteroporphyrins showed bathochromically shifted absorption bands, hypsochromically shifted fluorescence bands with decent quantum yields, more facile oxidation and more difficult reduction as compared to the corresponding phenothiazine embedded heteroporphyrins. DFT and TD-DFT studies were in support of the experimental observations.
在酸催化条件下，将一个等效的吩嗪基三吡喃与一个等效的适当的 2.5-双(羟甲基-对甲苯基)杂环缩合，合成了一系列含有一个吩嗪、两个吡咯和一个杂环（如呋喃、噻吩、硒吩和碲吩）的吩嗪内嵌杂卟啉，并将它们的结构、光谱和电化学性质与之前报道的吩噻嗪内嵌杂卟啉进行了比较、在酸催化条件下，将一个等量的吩嗪基三吡喃与一个等量的适当的 2、5-双（羟甲基-对甲苯基）杂环缩合合成了吩嗪基三吡喃和碲吩，并将它们的结构、光谱和电化学性质与之前报道的吩噻嗪嵌入杂卟啉进行了比较。嵌入吩噁嗪的硒卟啉的 X 射线晶体结构显示，与吩噁嗪分子相对的硒吩环指向大环核心的外侧，吩噁嗪单元与四个中碳原子定义的平均平面偏离 39.47° 角。用吩噁嗪单元取代吩噻嗪嵌入杂卟啉中的吩噻嗪单元会显著改变大环的电子特性，这反映在它们的光谱和电化学特性上。与相应的吩噻嗪内嵌杂卟啉相比，吩嗪内嵌杂卟啉的吸收光谱显示了浴色偏移的吸收带和次浴色偏移的荧光带，量子产率较高，更容易氧化和更难还原。DFT 和 TD-DFT 研究证实了实验观察结果。
{"title":"Synthesis, Structure, Spectral and Redox Properties of Phenoxazine Embedded Heteroporphyrins","authors":"Neha Tripathi, Mangalampalli Ravikanth","doi":"10.1002/ejoc.202401068","DOIUrl":"https://doi.org/10.1002/ejoc.202401068","url":null,"abstract":"A series of phenoxazine embedded heteroporphyrins containing one phenoxazine, two pyrroles and one heterocycle, such as furan, thiophene, selenophene and telluorophene, connected through four meso carbon atoms were synthesized by condensing one equivalent of phenoxazine-based tripyrrane with one equivalent of the appropriate 2,5-bis(hydroxymethyl-p-tolyl) heterocycle under acid-catalyzed conditions, and their structure, spectral and electrochemical properties were compared with those of previously reported phenothiazine embedded heteroporphyrins. The X-ray crystal structure of the phenoxazine embedded selenoporphyrin revealed that the selenophene ring, which is opposite phenoxazine moiety, points outward from the macrocyclic core, and the phenoxazine unit deviated by an angle of 39.47° from the mean plane defined by the four meso carbons atoms. The replacement of the phenothiazine unit in phenothiazine embedded heteroporphyrins with a phenoxazine unit led to significant alteration of the electronic properties of the macrocycles, as reflected in their spectral and electrochemical properties. The absorption spectra of phenoxazine embedded heteroporphyrins showed bathochromically shifted absorption bands, hypsochromically shifted fluorescence bands with decent quantum yields, more facile oxidation and more difficult reduction as compared to the corresponding phenothiazine embedded heteroporphyrins. DFT and TD-DFT studies were in support of the experimental observations.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588982","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}
Rabeb Ben Romdhane, Linhao Liu, Ridha Ben Salem, Henri Doucet
The Pd-catalyzed C4-arylation of 3,5-disubstituted isoxazoles via C-H bond functionalization has been largely described. By contrast, the reactivity of isoxazoles in C-H bond functionalization with both unsubstituted C4 and C5 positions remains largely unexplored. Herein, we report on the reactivity in Pd-catalyzed double C-H bond arylation of an isoxazole with unsubstituted C4 and C5 positions. Conditions for the palladium-catalyzed direct C4,C5-diarylation of ethyl isoxazole-3-carboxylate using aryl bromides as the aryl source are reported. This procedure tolerates several useful substituents on the aryl bromide such as nitrile, acetyl, formyl, benzoyl, alkoxycarbonyl, chloro, fluoro, trifluoromethyl, trifluoromethoxy, cyanomethyl,tertbutyl and methoxy at para- and meta-positions. Conversely, with ortho-substituted aryl bromides, mixtures of mono- and di-arylated isoxazoles were generally obtained. This methodology provides a simple one pot access to a wide variety of C4,C5-diarylated isoxazoles from commercially available substrates allowing to modify easily their biological properties.
{"title":"Palladium-Catalyzed C4,C5-Diarylation of Isoxazole-3-carboxylate by Double C–H Bond Functionalization","authors":"Rabeb Ben Romdhane, Linhao Liu, Ridha Ben Salem, Henri Doucet","doi":"10.1002/ejoc.202401036","DOIUrl":"https://doi.org/10.1002/ejoc.202401036","url":null,"abstract":"The Pd-catalyzed C4-arylation of 3,5-disubstituted isoxazoles via C-H bond functionalization has been largely described. By contrast, the reactivity of isoxazoles in C-H bond functionalization with both unsubstituted C4 and C5 positions remains largely unexplored. Herein, we report on the reactivity in Pd-catalyzed double C-H bond arylation of an isoxazole with unsubstituted C4 and C5 positions. Conditions for the palladium-catalyzed direct C4,C5-diarylation of ethyl isoxazole-3-carboxylate using aryl bromides as the aryl source are reported. This procedure tolerates several useful substituents on the aryl bromide such as nitrile, acetyl, formyl, benzoyl, alkoxycarbonyl, chloro, fluoro, trifluoromethyl, trifluoromethoxy, cyanomethyl,tertbutyl and methoxy at para- and meta-positions. Conversely, with ortho-substituted aryl bromides, mixtures of mono- and di-arylated isoxazoles were generally obtained. This methodology provides a simple one pot access to a wide variety of C4,C5-diarylated isoxazoles from commercially available substrates allowing to modify easily their biological properties.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574416","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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