Regio‐ and stereoselective β‐C(sp3)−H bond functionalizations of saturated nitrogen heterocycles, amines/amides are challenging and have emerged as an important topic of research in the area of C(sp3)−H activation. Herein, we have summarized various β‐C(sp3)−H activation/functionalization methods; this review provides an overview of various trending approaches for β‐C(sp3)−H bond activation/functionalization of saturated nitrogen heterocycles, amines/amides. The regio‐ and stereoselective β‐C(sp3)−H bond activation methods are classified based on the reaction pathways. The literature methods including directing group or ligand‐assisted transformations, reactions proceeding through enamine intermediate, redox‐neutral methods and other trending methods including photoredox and transitional metal‐free methods are discussed with recent updates.
{"title":"Regio‐ and Stereoselective β‐C(sp3)−H Activation/ Functionalization of Saturated Nitrogen Heterocycles, Amines and Amides","authors":"Sanjay Yadav , V. Murugesh , Surisetti Suresh","doi":"10.1002/adsc.202401398","DOIUrl":"10.1002/adsc.202401398","url":null,"abstract":"<div><div>Regio‐ and stereoselective <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H bond functionalizations of saturated nitrogen heterocycles, amines/amides are challenging and have emerged as an important topic of research in the area of C(<em>sp</em><sup>3</sup>)−H activation. Herein, we have summarized various <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H activation/functionalization methods; this review provides an overview of various trending approaches for <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H bond activation/functionalization of saturated nitrogen heterocycles, amines/amides. The regio‐ and stereoselective <em>β</em>‐C(<em>sp</em><sup>3</sup>)−H bond activation methods are classified based on the reaction pathways. The literature methods including directing group or ligand‐assisted transformations, reactions proceeding through enamine intermediate, redox‐neutral methods and other trending methods including photoredox and transitional metal‐free methods are discussed with recent updates.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401398"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991421","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anjali Dahiya , Kalyan Dhara , Jordan Garo , Julien Gicquiaud , Alexandre Karnat , Murielle Berlande , Philippe Hermange , Jean‐Marc Sotiropoulos , Patrick Y. Toullec
A chiral Brønsted acid‐catalyzed synthesis of axially chiral alkenes was developed via an enantioselective and para‐selective Friedel–Crafts reaction between phenols and 1‐alkynylnaphth‐2‐ols. This methodology features an efficient hydroarylation with high functional group tolerance, complete para‐selectivity, excellent yields (up to 99%), and enantioselectivities (up to 94% ee) in the presence of a N‐triflylphosphoramide catalyst. DFT calculations were performed to investigate para‐selectivity and results indicate that both kinetics and thermodynamics parameters are more favorable compared to ortho‐selectivity.
{"title":"Brønsted Acid‐Catalyzed Enantioselective and Para‐Selective Addition of Phenols to 1‐Alkynylnaphth‐2‐Ols","authors":"Anjali Dahiya , Kalyan Dhara , Jordan Garo , Julien Gicquiaud , Alexandre Karnat , Murielle Berlande , Philippe Hermange , Jean‐Marc Sotiropoulos , Patrick Y. Toullec","doi":"10.1002/adsc.202401457","DOIUrl":"10.1002/adsc.202401457","url":null,"abstract":"<div><div>A chiral Brønsted acid‐catalyzed synthesis of axially chiral alkenes was developed via an enantioselective and <em>para</em>‐selective Friedel–Crafts reaction between phenols and 1‐alkynylnaphth‐2‐ols. This methodology features an efficient hydroarylation with high functional group tolerance, complete <em>para</em>‐selectivity, excellent yields (up to 99%), and enantioselectivities (up to 94% ee) in the presence of a <em>N</em>‐triflylphosphoramide catalyst. DFT calculations were performed to investigate <em>para</em>‐selectivity and results indicate that both kinetics and thermodynamics parameters are more favorable compared to <em>ortho</em>‐selectivity.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401457"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maria Nicolas , Jan‐Dirk Küsters‐Spöring , Chiara Aufderheide , Helen Traving , Carina Ronja Kipp , Victoria S. Pfennig , Carsten Bolm , Petra Siegert , Dörte Rother
Chiral, vicinal diols are of high interest for academic research and industrial applications. For synthesizing chiral diols, enzymes are important catalysts due to their high selectivity and ability to work under tolerable temperature and no pressure. In this study, two consecutive enzyme‐catalyzed steps were used for the asymmetric synthesis of aliphatic, vicinal diols with high product concentrations and chiral purity. The reaction comprised a ligation step employing lyases and a subsequent reduction step using oxidoreductases. Either in an aqueous buffer or an organic solvent, the potentially biobased aldehydes acetaldehyde, propanal, butanal, and pentanal were used as substrates. Here, all possible stereoisomers of 2,3‐butanediol, 3,4‐hexanediol, 4,5‐octanediol, and 5,6‐decanediol were produced with isomeric content values between 72% and >99%, and concentrations between 4.1 and 115 mM. This work shows how four symmetric, chiral, vicinal diols can be synthesized by combining enzymes in a modular way, including exemplarily scaling.
{"title":"Enzymatic Asymmetric Synthesis of All Stereoisomers of Aliphatic, Vicinal Diols in Conventional and Non‐Conventional Media","authors":"Maria Nicolas , Jan‐Dirk Küsters‐Spöring , Chiara Aufderheide , Helen Traving , Carina Ronja Kipp , Victoria S. Pfennig , Carsten Bolm , Petra Siegert , Dörte Rother","doi":"10.1002/adsc.202401143","DOIUrl":"10.1002/adsc.202401143","url":null,"abstract":"<div><div>Chiral, vicinal diols are of high interest for academic research and industrial applications. For synthesizing chiral diols, enzymes are important catalysts due to their high selectivity and ability to work under tolerable temperature and no pressure. In this study, two consecutive enzyme‐catalyzed steps were used for the asymmetric synthesis of aliphatic, vicinal diols with high product concentrations and chiral purity. The reaction comprised a ligation step employing lyases and a subsequent reduction step using oxidoreductases. Either in an aqueous buffer or an organic solvent, the potentially biobased aldehydes acetaldehyde, propanal, butanal, and pentanal were used as substrates. Here, all possible stereoisomers of 2,3‐butanediol, 3,4‐hexanediol, 4,5‐octanediol, and 5,6‐decanediol were produced with <em>isomeric content</em> values between 72% and >99%, and concentrations between 4.1 and 115 mM. This work shows how four symmetric, chiral, vicinal diols can be synthesized by combining enzymes in a modular way, including exemplarily scaling.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401143"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Joanna Dybowska , Artur Przydacz , Anna Skrzyńska , Łukasz Albrecht
The manuscript describes a formal [10+2] higher‐order cycloaddition between 2‐arylideneindan‐1‐ones and α‐alkylidene azlactones as higherene precursors and higherenofiles respectively. The reaction is realized under Brønsted‐base catalysis utilizing the phase transfer catalysis approach. The key intermediate is an isobenzofulvene‐derived polyenolate which acts as a 10‐electron component in the higher‐order cycloaddition. By using this strategy, a series of structurally diverse compounds containing a polycyclic hydrocarbon scaffold was prepared in 79–99% yields. In addition, the potential of the obtained [10+2]‐cycloadducts has been confirmed by transformations, including the synthesis of a highly‐valuable α,α‐disubstituted N‐protected α‐aminoester.
.手稿描述了分别作为高烯前体和高烯赝品的 2-亚苄基茚-1-酮和α-亚烷基氮内酯之间的正式 [10+2] 高阶环加成反应。该反应是在布氏碱催化下利用相转移催化法实现的。关键的中间体是异苯乙烯衍生的聚烯酸酯，它在高阶环化反应中充当 10 电子元件。通过使用这种策略，制备出了一系列含有多环烃支架的结构多样的化合物，产率为 79-99%。此外，所获得的[10+2]-环加载产物的潜力已通过转化得到证实，包括合成了一种极具价值的α,α-二取代 N 保护α-氨基酯。
{"title":"PTC in the Polyenolate‐Mediated [10+2]‐Cycloaddition for the Synthesis of α,α‐Disubstituted Amino Acid Precursors","authors":"Joanna Dybowska , Artur Przydacz , Anna Skrzyńska , Łukasz Albrecht","doi":"10.1002/adsc.202400792","DOIUrl":"10.1002/adsc.202400792","url":null,"abstract":"<div><div>The manuscript describes a formal [10+2] higher‐order cycloaddition between 2‐arylideneindan‐1‐ones and α‐alkylidene azlactones as higherene precursors and higherenofiles respectively. The reaction is realized under Brønsted‐base catalysis utilizing the phase transfer catalysis approach. The key intermediate is an isobenzofulvene‐derived polyenolate which acts as a 10‐electron component in the higher‐order cycloaddition. By using this strategy, a series of structurally diverse compounds containing a polycyclic hydrocarbon scaffold was prepared in 79–99% yields. In addition, the potential of the obtained [10+2]‐cycloadducts has been confirmed by transformations, including the synthesis of a highly‐valuable α,α‐disubstituted <em>N</em>‐protected α‐aminoester.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202400792"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hui Meng , Zehua Wang , Ze‐Feng Xu , Chuan‐Ying Li
A rhodium (II)‐catalyzed transannulation reaction between aldehyde‐tethered N‐sulfonyl‐1,2,3‐triazoles and indoles was reported, which resulted in the formation of functionalized tetrahydroisoquinolin‐4‐ones. This reaction is notable for its broad substrate scope, including a variety of N‐sulfonyl‐1,2,3‐triazoles and different indoles. The addition of a protonic acid is essential for improving the yield of the desired tetrahydroisoquinolin‐4‐one products.
{"title":"Synthesis of Tetrahydroisoquinolin‐4‐Ones via Rh(II)‐Catalyzed One‐Pot Reaction of Aldehyde‐Tethered N‐Sulfonyl‐1,2,3‐Triazoles with Indoles","authors":"Hui Meng , Zehua Wang , Ze‐Feng Xu , Chuan‐Ying Li","doi":"10.1002/adsc.202401584","DOIUrl":"10.1002/adsc.202401584","url":null,"abstract":"<div><div>A rhodium (II)‐catalyzed transannulation reaction between aldehyde‐tethered <em>N</em>‐sulfonyl‐1,2,3‐triazoles and indoles was reported, which resulted in the formation of functionalized tetrahydroisoquinolin‐4‐ones. This reaction is notable for its broad substrate scope, including a variety of <em>N</em>‐sulfonyl‐1,2,3‐triazoles and different indoles. The addition of a protonic acid is essential for improving the yield of the desired tetrahydroisoquinolin‐4‐one products.</div></div>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 8","pages":"Article e202401584"},"PeriodicalIF":4.4,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Homogeneous transition-metal-catalyzed alkyne cascade cyclization reaction has attracted much attentions over the past decades. However, the relevant homogeneous transition-metal-catalyzed cyclization of allenynes has seldom been explored probably due to noticeable chemo-, regio-, and stereoselectivity. Described herein is an efficient homogeneous copper-catalyzed cycloisomerization reaction of allenynes, thus leading to a practical and atom-economic access to an array of valuable functionalized pyrroles by formal [3 + 2] cycloaddition via Cu-containing all-carbon 1,4-dipoles.
{"title":"Homogeneous Copper-Catalyzed Cycloisomerization Reaction of Allenynes: Rapid Access to Functionalized Pyrroles","authors":"Kua-Fei Wei, Xiu-Hong Zhu, Guang-Xin Ru, Wen-Bo Shen","doi":"10.1002/adsc.202500303","DOIUrl":"https://doi.org/10.1002/adsc.202500303","url":null,"abstract":"Homogeneous transition-metal-catalyzed alkyne cascade cyclization reaction has attracted much attentions over the past decades. However, the relevant homogeneous transition-metal-catalyzed cyclization of allenynes has seldom been explored probably due to noticeable chemo-, regio-, and stereoselectivity. Described herein is an efficient homogeneous copper-catalyzed cycloisomerization reaction of allenynes, thus leading to a practical and atom-economic access to an array of valuable functionalized pyrroles by formal [3 + 2] cycloaddition via Cu-containing all-carbon 1,4-dipoles.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"7 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pd-catalyzed reactions are among the most straightforward and efficient methods to proficiently build Csp2-Csp2 bonds. Nevertheless, thermal activation remains mandatory in most cases, which may decrease the compatibility with sensitive functional groups. In this context, improvements of conventional strategies must be an important source of research in order to enhance the applicability of such methods for building complex scaffolds. In this work, we contribute to this aim by implying visible-light as the sole energy source in a Pd-catalyzed rearrangement reaction involving N-tosylhydrazones and aryl halides. These mild reaction conditions efficiently allow oxidative addition, aryl migration and β-hydride elimination at room temperature, allowing the construction of various 1,1’ disubstituted olefins.
{"title":"Illuminating the Path of Rearrangement: Visible Light-Driven Pd-Catalyzed Substituted Olefins Synthesis","authors":"jenifer Sharshonov, Valentin Duchemann, Yuqian Sun, Christine Tran, Philippe Belmont, Abdallah HAMZE, Diana Lamaa, Etienne BRACHET","doi":"10.1002/adsc.202500161","DOIUrl":"https://doi.org/10.1002/adsc.202500161","url":null,"abstract":"Pd-catalyzed reactions are among the most straightforward and efficient methods to proficiently build Csp2-Csp2 bonds. Nevertheless, thermal activation remains mandatory in most cases, which may decrease the compatibility with sensitive functional groups. In this context, improvements of conventional strategies must be an important source of research in order to enhance the applicability of such methods for building complex scaffolds. In this work, we contribute to this aim by implying visible-light as the sole energy source in a Pd-catalyzed rearrangement reaction involving N-tosylhydrazones and aryl halides. These mild reaction conditions efficiently allow oxidative addition, aryl migration and β-hydride elimination at room temperature, allowing the construction of various 1,1’ disubstituted olefins.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lidia Prieto, Marcos Escolano, Daniel Gaviña, Luis Paredes-Soler, Santiago Díaz Oltra, Maria Sanchez-Rosello, Carlos del Pozo
A new family of fluorinated dihydropyrrolizinones has been synthesized starting from fluorinated enamino amides and aliphatic conjugated ketones. The reaction comprises a cross metathesis reaction followed by a tandem cycloaromatization/ enamine hydrolysis/ intramolecular Friedel-Crafts alkylation sequence. This pot-economical process takes place in good yields (35-67%), taking into account that it consists of four consecutive reactions. Aromatic enones are also good partners for this protocol although, in this case, the cross metathesis reaction has to be performed in a separated step.
{"title":"Pot-Economical Synthesis of Fluorinated Pyrrolizinone Derivatives","authors":"Lidia Prieto, Marcos Escolano, Daniel Gaviña, Luis Paredes-Soler, Santiago Díaz Oltra, Maria Sanchez-Rosello, Carlos del Pozo","doi":"10.1002/adsc.202500209","DOIUrl":"https://doi.org/10.1002/adsc.202500209","url":null,"abstract":"A new family of fluorinated dihydropyrrolizinones has been synthesized starting from fluorinated enamino amides and aliphatic conjugated ketones. The reaction comprises a cross metathesis reaction followed by a tandem cycloaromatization/ enamine hydrolysis/ intramolecular Friedel-Crafts alkylation sequence. This pot-economical process takes place in good yields (35-67%), taking into account that it consists of four consecutive reactions. Aromatic enones are also good partners for this protocol although, in this case, the cross metathesis reaction has to be performed in a separated step.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"76 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marcos Humanes, Manuel Ángel Fernández-Rodríguez, Patricia García-García
A selective, metal-free method for the synthesis of boron-functionalized polysubstituted naphthalenes via BCl₃-mediated cyclization of α-substituted o-alkynylstyrenes is described. The reaction exhibits broad substrate scope, tolerating various groups such as ethers, sulfides and halogens, and delivers high yields under mild conditions, even at gram scale. The resulting Bpin-functionalized naphthalenes serve as versatile building blocks, facilitating further transformations of the C–B bond into C–H, C–C, C–I, C–O, and C–N bonds, thereby increasing molecular complexity and enabling the design of more functionalized products.Notably, this sustainable and straightforward protocol selectively introduces the Bpin group at the sterically hindered α-carbon of the naphthalene framework, complementing C–H borylations of the naphthalene core, that preferentially occur at the β-position. As a result, the developed approach significantly broadens the accessibility of B-functionalized naphthalene derivatives for synthetic and application-oriented purposes.
{"title":"Synthesis of Polysubstitued Naphthalenes via Metal-free Borylative Cyclization of o-Alkynylstyrenes","authors":"Marcos Humanes, Manuel Ángel Fernández-Rodríguez, Patricia García-García","doi":"10.1002/adsc.202500244","DOIUrl":"https://doi.org/10.1002/adsc.202500244","url":null,"abstract":"A selective, metal-free method for the synthesis of boron-functionalized polysubstituted naphthalenes via BCl₃-mediated cyclization of α-substituted o-alkynylstyrenes is described. The reaction exhibits broad substrate scope, tolerating various groups such as ethers, sulfides and halogens, and delivers high yields under mild conditions, even at gram scale. The resulting Bpin-functionalized naphthalenes serve as versatile building blocks, facilitating further transformations of the C–B bond into C–H, C–C, C–I, C–O, and C–N bonds, thereby increasing molecular complexity and enabling the design of more functionalized products.\u0000Notably, this sustainable and straightforward protocol selectively introduces the Bpin group at the sterically hindered α-carbon of the naphthalene framework, complementing C–H borylations of the naphthalene core, that preferentially occur at the β-position. As a result, the developed approach significantly broadens the accessibility of B-functionalized naphthalene derivatives for synthetic and application-oriented purposes.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ni Dong, Xiao-Tian Zhang, Qin Tang, Jia-Xin Qian, Qi-Qi Luo, Long Cheng, Tian Cao, Xiang-Wei Liu
The synthesis of quinolones is a key technology for the preparation of active pharmaceutical ingredients. Herein we present a step‐economical methodology for streamlined synthesis of 4‐quinolones from a tandem process involving a reduction of nitroarenes, an aza‐Michael addition and an intramolecular Buchwald‐Hartwig amination. This strategy uses synthetically upstream nitroarenes as viable aniline surrogates and B2pin2 as an enabling organic reductant, producing a wide range of 4‐quinolones bearing different functional groups in a step‐economical fashion. The potential value of this protocol is highlighted by late‐stage installation of 4‐quinolone moiety onto bioactive compounds.
{"title":"Harnessing Nitroarenes in Streamlined Synthesis of 4‐Quinolones via Reductive C−N Coupling","authors":"Ni Dong, Xiao-Tian Zhang, Qin Tang, Jia-Xin Qian, Qi-Qi Luo, Long Cheng, Tian Cao, Xiang-Wei Liu","doi":"10.1002/adsc.202500393","DOIUrl":"https://doi.org/10.1002/adsc.202500393","url":null,"abstract":"The synthesis of quinolones is a key technology for the preparation of active pharmaceutical ingredients. Herein we present a step‐economical methodology for streamlined synthesis of 4‐quinolones from a tandem process involving a reduction of nitroarenes, an aza‐Michael addition and an intramolecular Buchwald‐Hartwig amination. This strategy uses synthetically upstream nitroarenes as viable aniline surrogates and B2pin2 as an enabling organic reductant, producing a wide range of 4‐quinolones bearing different functional groups in a step‐economical fashion. The potential value of this protocol is highlighted by late‐stage installation of 4‐quinolone moiety onto bioactive compounds.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"60 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143818943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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