Quinoxalin-2(1H)-ones and their derivatives constitute a privileged class of bioactive scaffolds with broad pharmacological potential, including anticancer, antibacterial, and neuroregulatory activities. Developing efficient and sustainable strategies for their molecular diversification under mild conditions remains a long-standing challenge in organic synthesis and medicinal chemistry. Here, we report a catalyst-free, light-driven CH functionalization strategy that exploits visible light and ambient air as the sole oxidant to achieve direct alkylation, arylation, and acylation of quinoxalin-2(1H)-ones. This operationally simple protocol features excellent substrate scope and functional group tolerance, delivering a wide range of structurally diverse quinoxalin-2(1H)-ones derivatives in a rapid and sustainable manner. Mechanistic investigations, supported by control experiments and spectroscopic studies, reveal that the transformation proceeds via the excitation of electron donor–acceptor complexes, which endows this system with the unique capability of enabling efficient CH functionalization without the need for any external catalyst.
{"title":"Catalyst-Free Visible-Light-Driven C?H Alkylation, Arylation, and Acylation of Quinoxalin-2(1H)-ones","authors":"Jing Cui, Yi-Tong Liu, Sheng-Bo Qi, Kai-Kai Niu, Ling-Bao Xing, Qing-Min Wang","doi":"10.1002/adsc.70228","DOIUrl":"https://doi.org/10.1002/adsc.70228","url":null,"abstract":"Quinoxalin-2(1<i>H</i>)-ones and their derivatives constitute a privileged class of bioactive scaffolds with broad pharmacological potential, including anticancer, antibacterial, and neuroregulatory activities. Developing efficient and sustainable strategies for their molecular diversification under mild conditions remains a long-standing challenge in organic synthesis and medicinal chemistry. Here, we report a catalyst-free, light-driven C<span></span>H functionalization strategy that exploits visible light and ambient air as the sole oxidant to achieve direct alkylation, arylation, and acylation of quinoxalin-2(1<i>H</i>)-ones. This operationally simple protocol features excellent substrate scope and functional group tolerance, delivering a wide range of structurally diverse quinoxalin-2(1<i>H</i>)-ones derivatives in a rapid and sustainable manner. Mechanistic investigations, supported by control experiments and spectroscopic studies, reveal that the transformation proceeds via the excitation of electron donor–acceptor complexes, which endows this system with the unique capability of enabling efficient C<span></span>H functionalization without the need for any external catalyst.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697115","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}
A copper catalyst‐controlled cascade annulation of CF 3 ‐imidoyl sulfoxonium ylides with activated nitriles has been disclosed, which enables the divergent synthesis of trifluoromethyl‐substituted pyrroles and quinolines. For the synthesis of pyrroles, the [3 + 2] annulation proceeds to give the multisubstituted pyrrole products. For the synthesis of quinolines, the CuI‐induced intramolecular cyclization is involved in the reaction with the cleavage of CCN bond.
{"title":"Catalyst‐Controlled Cascade Annulation of CF 3 ‐Imidoyl Sulfoxonium Ylides with Activated Nitriles for the Divergent Synthesis of Trifluoromethyl‐Substituted Pyrroles and Quinolines","authors":"Feng Han, Guangming Wei, Qihua Chen, Zhengkai Chen","doi":"10.1002/adsc.70220","DOIUrl":"https://doi.org/10.1002/adsc.70220","url":null,"abstract":"A copper catalyst‐controlled cascade annulation of CF <jats:sub>3</jats:sub> ‐imidoyl sulfoxonium ylides with activated nitriles has been disclosed, which enables the divergent synthesis of trifluoromethyl‐substituted pyrroles and quinolines. For the synthesis of pyrroles, the [3 + 2] annulation proceeds to give the multisubstituted pyrrole products. For the synthesis of quinolines, the CuI‐induced intramolecular cyclization is involved in the reaction with the cleavage of CCN bond.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145697253","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}
Carbonylation represents a straightforward and powerful strategy for installing carbonyl groups into organic molecules. However, the widespread adoption of carbon monoxide gas in laboratories is hampered by its toxicity, flammability, and smell‐less properties. To address these challenges, we developed a new carbon monoxide surrogate, inositol hexaformate (HFI), and demonstrated its utility in the palladium‐catalyzed aryloxycarbonylation of aryl bromides with phenols. Notably, HFI efficiently releases six equivalents of carbon monoxide, showing a significant improvement in efficiency over commonly used formate surrogates. This work provides a practical and robust method for conducting carbonylation reactions, which is expected to broaden the accessibility of this important transformation in synthetic chemistry.
{"title":"Palladium‐Catalyzed Aryloxycarbonylayion of Aryl Bromides with Phenols Using Inositol Hexaformate as an Efficient CO Source","authors":"Zhen‐Wei Liu, Yong‐Wang Huo, Xiao‐Feng Wu","doi":"10.1002/adsc.70261","DOIUrl":"https://doi.org/10.1002/adsc.70261","url":null,"abstract":"Carbonylation represents a straightforward and powerful strategy for installing carbonyl groups into organic molecules. However, the widespread adoption of carbon monoxide gas in laboratories is hampered by its toxicity, flammability, and smell‐less properties. To address these challenges, we developed a new carbon monoxide surrogate, <jats:italic>inositol hexaformate</jats:italic> (HFI), and demonstrated its utility in the palladium‐catalyzed aryloxycarbonylation of aryl bromides with phenols. Notably, HFI efficiently releases six equivalents of carbon monoxide, showing a significant improvement in efficiency over commonly used formate surrogates. This work provides a practical and robust method for conducting carbonylation reactions, which is expected to broaden the accessibility of this important transformation in synthetic chemistry.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"115 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680742","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}
A practical, highly atom‐economical and switchable α ‐C(sp 2 )−H (di)thiocarbamation/chromone annulation reaction for the divergent synthesis of two types of 3‐substituted chromones has been developed. A variety of 3‐dithiocarbamyl chromones and 3‐carbamothioyl chromones were constructed efficiently from readily available o ‐hydroxyphenylenaminones ( o ‐HPEs) and carbon disulfide (CS 2 ) via KIO 3 /DTBP cooperative catalytic oxidation. Notably, this transformation proceeds efficiently by recycling by‐product dimethylamine and employing equivalent amount of CS 2 . This strategy features high atom economy, mild reaction conditions, broad substrate scope, gram‐scale preparation and further derivatization.
{"title":"Switchable Divergent Synthesis of 3‐Dithiocarbamyl and 3‐Carbamothioyl Chromones Through Chromone Annulation Reactions of o ‐Hydroxyenaminones With CS 2","authors":"Huimin Hu, Yuanzheng Wei, Ying Xu, Menglin Peng, Shaolin Yang, Yu Xu, Yu Zhang, Li Chen, Fuchao Yu","doi":"10.1002/adsc.70260","DOIUrl":"https://doi.org/10.1002/adsc.70260","url":null,"abstract":"A practical, highly atom‐economical and switchable <jats:italic>α</jats:italic> ‐C(sp <jats:sup>2</jats:sup> )−H (di)thiocarbamation/chromone annulation reaction for the divergent synthesis of two types of 3‐substituted chromones has been developed. A variety of 3‐dithiocarbamyl chromones and 3‐carbamothioyl chromones were constructed efficiently from readily available <jats:italic>o</jats:italic> ‐hydroxyphenylenaminones ( <jats:italic>o</jats:italic> ‐HPEs) and carbon disulfide (CS <jats:sub>2</jats:sub> ) <jats:italic>via</jats:italic> KIO <jats:sub>3</jats:sub> /DTBP cooperative catalytic oxidation. Notably, this transformation proceeds efficiently by recycling by‐product dimethylamine and employing equivalent amount of CS <jats:sub>2</jats:sub> . This strategy features high atom economy, mild reaction conditions, broad substrate scope, gram‐scale preparation and further derivatization.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"138 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680739","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}
Developing efficient methods to incorporate a primary amino group onto small molecules is of great importance in pharmaceutical and agrochemical fields. This significance becomes even more pronounced when it comes to accessing their corresponding 15 N isotopologs. Here, we present a mild, transition‐metal‐free, and stoichiometric oxidant‐free amination protocol for fluoroenones by employing user‐friendly ammonium carbonate as the primary amino source. The protocol demonstrates high atom economy by directly converting starting materials into the α ‐aminoenones. When the ammonia surrogate is replaced with a readily available combination of 15 NH 4 Cl and Na 2 CO 3 , a variety of completely 15 N‐labeled primary α ‐aminoenones can be synthesized with excellent functional group compatibility. The critical role of iodine in enhancing primary amination of fluoroenones is revealed by the transient formation of a more reactive iodinated enone, which facilitates downstream nucleophilic amination. Furthermore, the protocol exhibits robust scalability and is compatible with biologically and naturally relevant molecules. Molecular iodine is demonstrated as an inexpensive, environmentally benign, and easy‐to‐handle additive to pursue primary amination.
{"title":"Primary Amination of Enones Using Inorganic Ammonium Salts and Nitrogen Isotope Incorporation","authors":"Shu‐Ji Gao, Shuang Liu, Ming‐Yang Gu, Yi‐Fan Ji, Danhua Ge, Zhi‐Liang Shen, Mengtao Ma, Xue‐Qiang Chu","doi":"10.1002/adsc.70188","DOIUrl":"https://doi.org/10.1002/adsc.70188","url":null,"abstract":"Developing efficient methods to incorporate a primary amino group onto small molecules is of great importance in pharmaceutical and agrochemical fields. This significance becomes even more pronounced when it comes to accessing their corresponding <jats:sup>15</jats:sup> N isotopologs. Here, we present a mild, transition‐metal‐free, and stoichiometric oxidant‐free amination protocol for fluoroenones by employing user‐friendly ammonium carbonate as the primary amino source. The protocol demonstrates high atom economy by directly converting starting materials into the <jats:italic>α</jats:italic> ‐aminoenones. When the ammonia surrogate is replaced with a readily available combination of <jats:sup>15</jats:sup> NH <jats:sub>4</jats:sub> Cl and Na <jats:sub>2</jats:sub> CO <jats:sub>3</jats:sub> , a variety of completely <jats:sup>15</jats:sup> N‐labeled primary <jats:italic>α</jats:italic> ‐aminoenones can be synthesized with excellent functional group compatibility. The critical role of iodine in enhancing primary amination of fluoroenones is revealed by the transient formation of a more reactive iodinated enone, which facilitates downstream nucleophilic amination. Furthermore, the protocol exhibits robust scalability and is compatible with biologically and naturally relevant molecules. Molecular iodine is demonstrated as an inexpensive, environmentally benign, and easy‐to‐handle additive to pursue primary amination.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680740","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}
Sulfur(VI) fluoride exchange (SuFEx) has emerged as a powerful click chemistry platform for covalent bond formation, with broad applications in drug discovery, polymer science, and bioconjugation. Among the diverse SuFEx linkers developed in recent years, sulfonimidoyl fluorides (RN=S(O)F) have gained prominence due to their tunable electrophilicity, multifunctional modifiable sites, and the presence of chiral sulfur(VI) centers. This reagent exhibits exceptional reactivity in stereospecific SuFEx transformations, offering not only an efficient strategy for the synthesis of enantioenriched sulfur compounds but also a versatile foundation for covalent drug discovery and chemical probe development. This review systematically summarizes recent advances in sulfonimidoyl fluoride chemistry, with an emphasis on the construction of chiral S(VI) centers and stereocontrolled SuFEx reactions. Despite the limited literature in this nascent field, key breakthroughs and discuss future research directions, is consolidated providing forward‐looking perspectives to stimulate further progress in stereospecific SuFEx chemistry.
{"title":"Recent Advances and Prospect in Stereospecific Sulfur(VI) Fluoride Exchange Chemistry","authors":"He‐sen Huang, Zhuo Tang, Guang‐xun Li","doi":"10.1002/adsc.70171","DOIUrl":"https://doi.org/10.1002/adsc.70171","url":null,"abstract":"Sulfur(VI) fluoride exchange (SuFEx) has emerged as a powerful click chemistry platform for covalent bond formation, with broad applications in drug discovery, polymer science, and bioconjugation. Among the diverse SuFEx linkers developed in recent years, <jats:italic>sulfonimidoyl fluorides</jats:italic> (RN=S(O)F) have gained prominence due to their tunable electrophilicity, multifunctional modifiable sites, and the presence of chiral sulfur(VI) centers. This reagent exhibits exceptional reactivity in stereospecific SuFEx transformations, offering not only an efficient strategy for the synthesis of enantioenriched sulfur compounds but also a versatile foundation for covalent drug discovery and chemical probe development. This review systematically summarizes recent advances in sulfonimidoyl fluoride chemistry, with an emphasis on the construction of chiral S(VI) centers and stereocontrolled SuFEx reactions. Despite the limited literature in this nascent field, key breakthroughs and discuss future research directions, is consolidated providing forward‐looking perspectives to stimulate further progress in stereospecific SuFEx chemistry.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"57 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145680741","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}
Nidhi Saini, Chhavi Khajuria, Khushboo Gupta, Vinod K. Singh
An efficient regio‐ and enantioselective synthesis of pyrano[3,2‐ c ]coumarins has been developed via a [3 + 3] annulation reaction between α ‐CF 3 alkynyl ketimines and 4‐hydroxycoumarins. The reaction proceeds via a squaramide‐catalyzed stereospecific Mannich reaction followed by a Lewis acid‐mediated annulation, enabling excellent control of both regio‐ and enantioselectivity. Notably, this represents the first enantioselective synthesis of pyrano[3,2‐ c ]coumarin derivatives bearing an aza‐quaternary stereocenter. The methodology exhibits broad substrate compatibility with both steric and electronic variations. Practicality of the protocol is demonstrated by scale‐up reaction as well as diverse downstream functionalizations.
{"title":"Enantioselective Synthesis of Pyrano[3,2‐ c ]coumarin Bearing Aza‐Quaternary Stereocenter via [3 + 3] Annulation Reaction with α ‐CF 3 Alkynyl Ketimines and 4‐Hydroxycoumarins","authors":"Nidhi Saini, Chhavi Khajuria, Khushboo Gupta, Vinod K. Singh","doi":"10.1002/adsc.70263","DOIUrl":"https://doi.org/10.1002/adsc.70263","url":null,"abstract":"An efficient regio‐ and enantioselective synthesis of pyrano[3,2‐ <jats:italic>c</jats:italic> ]coumarins has been developed via a [3 + 3] annulation reaction between <jats:italic>α</jats:italic> ‐CF <jats:sub>3</jats:sub> alkynyl ketimines and 4‐hydroxycoumarins. The reaction proceeds via a squaramide‐catalyzed stereospecific Mannich reaction followed by a Lewis acid‐mediated annulation, enabling excellent control of both regio‐ and enantioselectivity. Notably, this represents the first enantioselective synthesis of pyrano[3,2‐ <jats:italic>c</jats:italic> ]coumarin derivatives bearing an aza‐quaternary stereocenter. The methodology exhibits broad substrate compatibility with both steric and electronic variations. Practicality of the protocol is demonstrated by scale‐up reaction as well as diverse downstream functionalizations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"55 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145673572","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}
Yuqian Sun, Biao Cheng, Bin Li, Xinying Zhang, Xuesen Fan
Both isoindolin‐1‐one and isoxazolidine are privileged scaffolds in developing new pharmaceuticals and functional materials. Presented herein is a novel synthesis of CF 3 ‐ isoxazolidine‐fused isoindolin‐1‐ones through the cascade reaction of N ‐hydroxybenzamides with CF 3 ‐ynones. The formation of product is initiated by aryl CH bond metalation and insertion of the triple bond, followed by protodemetalation, intramolecular aza ‐Michael addition, and oxo ‐nucleophilic addition. In this cascade process, the N ‐hydroxyamide group plays a triple role by acting as: 1) directing group for CH bond metalation; 2) N ‐nucleophilic site for isoindolin‐1‐one ring formation; and 3) O ‐nucleophilic site for isoxazolidine ring formation. To the authors' knowledge, this is the first report on the concurrent construction of these two privileged cyclic scaffolds in one pot. In addition, the products thus formed can be transformed into several valuable compounds through easy‐to‐run derivations by taking advantage of the rich chemistry of the functional groups embedded therein.
{"title":"Cascade Annulation of N ‐Hydroxybenzamides with CF 3 ‐Ynones Leading to CF 3 ‐Isoxazolidine‐Fused Isoindolin‐1‐Ones","authors":"Yuqian Sun, Biao Cheng, Bin Li, Xinying Zhang, Xuesen Fan","doi":"10.1002/adsc.70051","DOIUrl":"https://doi.org/10.1002/adsc.70051","url":null,"abstract":"Both isoindolin‐1‐one and isoxazolidine are privileged scaffolds in developing new pharmaceuticals and functional materials. Presented herein is a novel synthesis of CF <jats:sub>3</jats:sub> ‐ isoxazolidine‐fused isoindolin‐1‐ones through the cascade reaction of <jats:italic>N</jats:italic> ‐hydroxybenzamides with CF <jats:sub>3</jats:sub> ‐ynones. The formation of product is initiated by aryl CH bond metalation and insertion of the triple bond, followed by protodemetalation, intramolecular <jats:italic>aza</jats:italic> ‐Michael addition, and <jats:italic>oxo</jats:italic> ‐nucleophilic addition. In this cascade process, the <jats:italic>N</jats:italic> ‐hydroxyamide group plays a triple role by acting as: 1) directing group for CH bond metalation; 2) <jats:italic>N</jats:italic> ‐nucleophilic site for isoindolin‐1‐one ring formation; and 3) <jats:italic>O</jats:italic> ‐nucleophilic site for isoxazolidine ring formation. To the authors' knowledge, this is the first report on the concurrent construction of these two privileged cyclic scaffolds in one pot. In addition, the products thus formed can be transformed into several valuable compounds through easy‐to‐run derivations by taking advantage of the rich chemistry of the functional groups embedded therein.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"124 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145673946","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}
Amjad Ayad Qatran Al‐Khdhairawi, Tengrui Yuan, Kristof Van Hecke, Lucile Jouffroy, Johan M. Winne
A general and stereoselective synthesis of highly substituted cyclopentylamine scaffolds is reported starting from various N‐alkenyl‐amides. The reaction involves the generation of an aurated dithioallyl cation which undergoes a classical stepwise (3 + 2) allyl cation cycloaddition with a range of enamide substrates. The close coordination of the reactive intermediates with the well‐defined gold(I)‐catalyst results in a reactivity and selectivity profile that can be readily rationalized on the basis of a nonconcerted carbocationic cycloaddition reaction, and some remarkable counterion effects are seen to effect the chemoselectivity of the overall process.
{"title":"Stereoselective De Novo Synthesis of Substituted Cyclopentanes via a Gold(I)‐Catalyzed (3 + 2) Cycloaddition of Enamides","authors":"Amjad Ayad Qatran Al‐Khdhairawi, Tengrui Yuan, Kristof Van Hecke, Lucile Jouffroy, Johan M. Winne","doi":"10.1002/adsc.70182","DOIUrl":"https://doi.org/10.1002/adsc.70182","url":null,"abstract":"A general and stereoselective synthesis of highly substituted cyclopentylamine scaffolds is reported starting from various N‐alkenyl‐amides. The reaction involves the generation of an aurated dithioallyl cation which undergoes a classical stepwise (3 + 2) allyl cation cycloaddition with a range of enamide substrates. The close coordination of the reactive intermediates with the well‐defined gold(I)‐catalyst results in a reactivity and selectivity profile that can be readily rationalized on the basis of a nonconcerted carbocationic cycloaddition reaction, and some remarkable counterion effects are seen to effect the chemoselectivity of the overall process.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"246 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145673942","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}
Described herein are two annulative functionalization approaches to novel indolizines leveraging a domino aldol condensation‐vinylogous aldol condensation procedure to construct the pyridine moiety of indolizines, enabling installation of an alkyl, an aryl, or an alkoxy group at the C7 position and an acyl group at the C5 position of indolizine framework. In the first approach, aldehyde oxidatively generated in situ from trialkylamine participated in a [4 + 2] annulation process with N ‐substituted pyrrole‐2‐carboxaldehydes to give rise to 5‐acylindolizines. In the second approach, the use of various aldehydes as reaction partners in this protocol allowed for the introduction of a wide range of substituents at the C7 site of indolizines.
{"title":"Exploring the Uncharted Indolizine Chemical Space: Construction of 5‐Acylindolizines via a Domino Aldol–Vinylogous Aldol Process","authors":"Dohui Ku, Sunhee Lee, Ikyon Kim","doi":"10.1002/adsc.70201","DOIUrl":"https://doi.org/10.1002/adsc.70201","url":null,"abstract":"Described herein are two annulative functionalization approaches to novel indolizines leveraging a domino aldol condensation‐vinylogous aldol condensation procedure to construct the pyridine moiety of indolizines, enabling installation of an alkyl, an aryl, or an alkoxy group at the C7 position and an acyl group at the C5 position of indolizine framework. In the first approach, aldehyde oxidatively generated in situ from trialkylamine participated in a [4 + 2] annulation process with <jats:italic>N</jats:italic> ‐substituted pyrrole‐2‐carboxaldehydes to give rise to 5‐acylindolizines. In the second approach, the use of various aldehydes as reaction partners in this protocol allowed for the introduction of a wide range of substituents at the C7 site of indolizines.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"157 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145673943","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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