A divergent Ru(II)-catalyzed protocol for the efficient transformation of β-ketosulfoxonium ylides into two distinct molecular scaffolds under mild conditions has been developed. In the presence of [Ru(p-cymene)Cl2]2 and Cu(OAc)2·H2O, selective amidation with primary or secondary amines provides biologically relevant α-ketoamides, whereas homocoupling in the absence of amines affords less explored α,α,β-tricarbonyl sulfoxonium ylides. Both pathways proceed via a common Ru-carbene intermediate and exhibit broad substrate scope and functional group tolerance. The synthetic utility is further demonstrated by downstream transformations, including heterocycle formation and late-stage modifications.
{"title":"Ru(II)-Catalyzed Divergent Amidation and Homocoupling of β-Ketosulfoxonium Ylides: Selective Access to α-Ketoamides and α,α,β-Tricarbonyl Sulfoxonium Ylides","authors":"Ajay Kant Gola, Satyendra Kumar Pandey","doi":"10.1002/adsc.70264","DOIUrl":"https://doi.org/10.1002/adsc.70264","url":null,"abstract":"A divergent Ru(II)-catalyzed protocol for the efficient transformation of β-ketosulfoxonium ylides into two distinct molecular scaffolds under mild conditions has been developed. In the presence of [Ru(<i>p</i>-cymene)Cl<sub>2</sub>]<sub>2</sub> and Cu(OAc)<sub>2</sub>·H<sub>2</sub>O, selective amidation with primary or secondary amines provides biologically relevant α-ketoamides, whereas homocoupling in the absence of amines affords less explored α,α,β-tricarbonyl sulfoxonium ylides. Both pathways proceed via a common Ru-carbene intermediate and exhibit broad substrate scope and functional group tolerance. The synthetic utility is further demonstrated by downstream transformations, including heterocycle formation and late-stage modifications.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711385","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}
An acid-functionalized ionic liquid-catalyzed annulation of 2-arylaniline and diazo compound was developed via cascade Wolff rearrangement, which is different from the precedent transformations mediated by metal or acid involving a NH bond insertion. A spectrum of diverse diazos were well compatible, in particular, the unsymmetrical diazos provided exclusive product through selective Wolff rearrangement. Mechanistic studies disclosed that the reaction proceeded through tandem Wolff rearrangement, nucleophilic addition, oxidation, and cyclization via the electrostatic interaction and hydrogen-bonding effect of ionic liquid.
{"title":"Ionic Liquid-Catalyzed Annulation of 2-Arylanilines and Diazo Compounds via Wolff Rearrangement","authors":"Shanshan Liu, Weiwei Dong, Zhenzhen Li, Pingjun Zhang, Yaoyao Zhang, Cong Yan, Lin-Yu Jiao","doi":"10.1002/adsc.70227","DOIUrl":"https://doi.org/10.1002/adsc.70227","url":null,"abstract":"An acid-functionalized ionic liquid-catalyzed annulation of 2-arylaniline and diazo compound was developed via cascade Wolff rearrangement, which is different from the precedent transformations mediated by metal or acid involving a N<span></span>H bond insertion. A spectrum of diverse diazos were well compatible, in particular, the unsymmetrical diazos provided exclusive product through selective Wolff rearrangement. Mechanistic studies disclosed that the reaction proceeded through tandem Wolff rearrangement, nucleophilic addition, oxidation, and cyclization via the electrostatic interaction and hydrogen-bonding effect of ionic liquid.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"144 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145711384","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}
The selective functionalization of indoles using methanol via borrowing hydrogen (BH) and interrupted borrowing hydrogen (I‐BH) pathways offers a sustainable approach to access value‐added molecules. Herein, the synthesis of a series of benzimidazole‐functionalized cyclometalated (NC)‐Ru(II) and (NN)‐Ru(II) complexes and their application in the chemodivergent functionalization of indoles with methanol are reported, affording either C3‐methylated indoles or bis(indolyl)methanes (BIMs). The product selectivity was governed by the hydricity of the Ru–H species, which was effectively tuned by ligand backbone modification. This varying catalytic behavior of these complexes under consideration toward the selective formation of different products was fairly understood by analyzing their electronic properties based on electrochemical and density functional theory studies. Additionally, the electron‐rich (NC)‐Ru complex facilitated the α‐methylation of phenylacetonitrile under relatively mild conditions. Finally, an array of control experiments and the identification of different intermediates aided in establishing the proposed mechanism.
{"title":"Hydricity Modulated Methylation of Indoles and Nitriles Using Methanol: Selective Synthesis of C3‐Methylated Indoles, Bisindolylmethanes, and α‐Methylated Nitriles","authors":"Manoj Pradhan, Adarsha Mandal, Prabhakar Tiwari, Ishani Borthakur, Manash Protim Borpuzari, Sabuj Kundu","doi":"10.1002/adsc.70224","DOIUrl":"https://doi.org/10.1002/adsc.70224","url":null,"abstract":"The selective functionalization of indoles using methanol via borrowing hydrogen (BH) and interrupted borrowing hydrogen (I‐BH) pathways offers a sustainable approach to access value‐added molecules. Herein, the synthesis of a series of benzimidazole‐functionalized cyclometalated (NC)‐Ru(II) and (NN)‐Ru(II) complexes and their application in the chemodivergent functionalization of indoles with methanol are reported, affording either C3‐methylated indoles or bis(indolyl)methanes (BIMs). The product selectivity was governed by the hydricity of the Ru–H species, which was effectively tuned by ligand backbone modification. This varying catalytic behavior of these complexes under consideration toward the selective formation of different products was fairly understood by analyzing their electronic properties based on electrochemical and density functional theory studies. Additionally, the electron‐rich (NC)‐Ru complex facilitated the α‐methylation of phenylacetonitrile under relatively mild conditions. Finally, an array of control experiments and the identification of different intermediates aided in establishing the proposed mechanism.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"57 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704255","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}
Amides and sulfoximines are pivotal structural motifs in pharmaceuticals and agrochemicals; however, sustainable and direct methods for their incorporation remain underdeveloped. Herein, a metal‐ and additive‐free protocol is presented for the efficient synthesis of N ‐acyl sulfoximines via selective NC bond cleavage of amides, utilizing bench‐stable N‐ acyl saccharin as an acylating agent for NH‐sulfoximines. This transformation proceeds under mild conditions using green solvents and exhibits a broad substrate scope encompassing natural products and drug derivatives. Notably, the method is compatible with both batch and continuous‐flow platforms, achieving a significant reduction in reaction time from 24 h to 15 min. The process offers high yields, excellent functional group tolerance, and gram‐scale scalability. Furthermore, the recovery of recyclable saccharin enhances atom economy and minimizes waste generation.
{"title":"Metal‐Free Chemoselective Amide Bond Cleavage for the Synthesis of N ‐Acyl Sulfoximines in Batch and Flow","authors":"Karthick Govindan, Nian‐Qi Chen, Wei‐Yu Lin","doi":"10.1002/adsc.70163","DOIUrl":"https://doi.org/10.1002/adsc.70163","url":null,"abstract":"Amides and sulfoximines are pivotal structural motifs in pharmaceuticals and agrochemicals; however, sustainable and direct methods for their incorporation remain underdeveloped. Herein, a metal‐ and additive‐free protocol is presented for the efficient synthesis of <jats:italic>N</jats:italic> ‐acyl sulfoximines via selective NC bond cleavage of amides, utilizing bench‐stable <jats:italic>N‐</jats:italic> acyl saccharin as an acylating agent for NH‐sulfoximines. This transformation proceeds under mild conditions using green solvents and exhibits a broad substrate scope encompassing natural products and drug derivatives. Notably, the method is compatible with both batch and continuous‐flow platforms, achieving a significant reduction in reaction time from 24 h to 15 min. The process offers high yields, excellent functional group tolerance, and gram‐scale scalability. Furthermore, the recovery of recyclable saccharin enhances atom economy and minimizes waste generation.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"3 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704256","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}
Enantioselective regiodivergent cascade reactions remain a significant challenge due to the dual requirement of achieving precise control over both regioselectivity and stereoselectivity. Herein, a quinine‐derived bifunctional catalyst‐driven strategy is presented for constructing the diverse asymmetric polycyclic spiro‐pyrazolone scaffolds in a cascade manner. The cascade reaction is initiated by the asymmetric vinylogous Michael addition (VMA) of arylidene pyrazolones to the indandione‐derived acceptors, followed by regioselective transformations that lead to structurally diverse products. The divergent reaction outcomes are governed by the interaction between the in situ generated conjugate acid of the catalyst and the anionic intermediate (VMA adduct). These outcomes are further modulated by adjustments in the reaction conditions, particularly the polarity of the solvent. In toluene, the reaction predominantly yields the cage product with excellent regio‐ and enantioselectivity via a cascade pathway involving asymmetric VMA/acetalization/oxa‐Michael/Michael addition. In contrast, in MeCN, the reaction proceeds through an asymmetric VMA/proton transfer/aldol/acetalization, furnishing the fused product. Mechanistic studies reveal that the formation of the fused product involves an unusual and reversible reaction pathway. Specifically, the catalyst‐controlled 1,6‐conjugate addition of 1,3‐indandione to the diene intermediate occurs under optimal conditions. This strategy demonstrates a versatile foundation for asymmetric regiodivergent cascade reactions.
{"title":"Solvent‐Enabled Organocatalyst‐Assisted Enantioselective Regiodivergent Cascade Reactions: Overriding Intrinsic Reactivity of Vinylogous Pyrazolones","authors":"Ganesh Shantaram Khomane, Tzu‐Chun Yen, Gangababu Marri, Yi‐Ru Chen, Pin‐Ching Wang, Wenwei Lin","doi":"10.1002/adsc.70173","DOIUrl":"https://doi.org/10.1002/adsc.70173","url":null,"abstract":"Enantioselective regiodivergent cascade reactions remain a significant challenge due to the dual requirement of achieving precise control over both regioselectivity and stereoselectivity. Herein, a quinine‐derived bifunctional catalyst‐driven strategy is presented for constructing the diverse asymmetric polycyclic spiro‐pyrazolone scaffolds in a cascade manner. The cascade reaction is initiated by the asymmetric vinylogous Michael addition (VMA) of arylidene pyrazolones to the indandione‐derived acceptors, followed by regioselective transformations that lead to structurally diverse products. The divergent reaction outcomes are governed by the interaction between the in situ generated conjugate acid of the catalyst and the anionic intermediate (VMA adduct). These outcomes are further modulated by adjustments in the reaction conditions, particularly the polarity of the solvent. In toluene, the reaction predominantly yields the cage product with excellent regio‐ and enantioselectivity via a cascade pathway involving asymmetric VMA/acetalization/oxa‐Michael/Michael addition. In contrast, in MeCN, the reaction proceeds through an asymmetric VMA/proton transfer/aldol/acetalization, furnishing the fused product. Mechanistic studies reveal that the formation of the fused product involves an unusual and reversible reaction pathway. Specifically, the catalyst‐controlled 1,6‐conjugate addition of 1,3‐indandione to the diene intermediate occurs under optimal conditions. This strategy demonstrates a versatile foundation for asymmetric regiodivergent cascade reactions.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"140 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704548","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 dual‐catalytic metallaphotoredox strategy repurposes sulfonamides as sulfonylating reagents via radical cascades, leveraging copper's dual role as photoredox mediator and coupling catalyst. Exemplified by iodosulfonylation of alkynes, the protocol achieves in situ sulfonamide diazotization to generate sulfonyl radicals, followed by regioselective addition to alkynes and copper‐catalyzed iodination. This all‐in‐one strategy eliminates the need for sulfonamide prefunctionalization, offering step‐economy, operational simplicity, and broad functional group tolerance.
{"title":"Late‐Stage Deaminative Radical Diversification of Sulfonamides via CuI/Photoredox Synergy: A Direct Strategy for (E)‐β‐Iodovinyl Sulfones","authors":"Cheng‐Liang Liu, Jia Liu, Jia‐Ying Dai, Zi‐Rui Kuang, Zhi‐Xing Liu, Qian Yan, Zhi‐Wei Li, Jiang‐Sheng Li","doi":"10.1002/adsc.70068","DOIUrl":"https://doi.org/10.1002/adsc.70068","url":null,"abstract":"A dual‐catalytic metallaphotoredox strategy repurposes sulfonamides as sulfonylating reagents via radical cascades, leveraging copper's dual role as photoredox mediator and coupling catalyst. Exemplified by iodosulfonylation of alkynes, the protocol achieves in situ sulfonamide diazotization to generate sulfonyl radicals, followed by regioselective addition to alkynes and copper‐catalyzed iodination. This all‐in‐one strategy eliminates the need for sulfonamide prefunctionalization, offering step‐economy, operational simplicity, and broad functional group tolerance.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704253","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}
Fang‐Jiang Cui, Dong‐Dong Liang, Xiang‐Fei Kong, Dong‐Liang Mo
We describe a facile method to prepare a variety of imidazo‐fuzed pyrazino[2,1‐ b ]quinazolinone scaffolds in good to excellent yields through gold(I)‐catalyzed and base‐mediated intramolecular hydroamination reactions of N3‐alkynyl quinazolinone tethered imidazoles. It was found that 5‐methylene imidazo‐fuzed pyrazino[2,1‐ b ]quinazolinones were obtained under gold(I)‐catalyzed conditions, while base‐mediated conditions afforded 5‐alkyl imidazo‐fuzed pyrazino[2,1‐ b ]quinazolinones. The reaction could be easily prepared on a gram scales. More importantly, the prepared 5‐methylene imidazo‐fuzed pyrazino[2,1‐ b ]quinazolinones could be applied in the various metal ions recognition based on their fluorescence properties.
{"title":"Synthesis of Imidazo‐Fuzed Pyrazino[2,1‐ b ]quinazolinones Through Gold(I)‐ and Base‐Promoted Intramolecular Hydroamination Cyclization","authors":"Fang‐Jiang Cui, Dong‐Dong Liang, Xiang‐Fei Kong, Dong‐Liang Mo","doi":"10.1002/adsc.70250","DOIUrl":"https://doi.org/10.1002/adsc.70250","url":null,"abstract":"We describe a facile method to prepare a variety of imidazo‐fuzed pyrazino[2,1‐ <jats:italic>b</jats:italic> ]quinazolinone scaffolds in good to excellent yields through gold(I)‐catalyzed and base‐mediated intramolecular hydroamination reactions of N3‐alkynyl quinazolinone tethered imidazoles. It was found that 5‐methylene imidazo‐fuzed pyrazino[2,1‐ <jats:italic>b</jats:italic> ]quinazolinones were obtained under gold(I)‐catalyzed conditions, while base‐mediated conditions afforded 5‐alkyl imidazo‐fuzed pyrazino[2,1‐ <jats:italic>b</jats:italic> ]quinazolinones. The reaction could be easily prepared on a gram scales. More importantly, the prepared 5‐methylene imidazo‐fuzed pyrazino[2,1‐ <jats:italic>b</jats:italic> ]quinazolinones could be applied in the various metal ions recognition based on their fluorescence properties.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"260 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704547","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}
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}
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