Direct hydroalkylation of ynazoles, facilitating the efficient synthesis of linear N-β-vinylazoles, is accomplished through the functionalization of sp3 C-H bonds using trace amounts of dioxygen as an initiator. This reagent-free method eliminates the need for exogenous reagents and proceeds through a radical chain mechanism involving dual hydrogen atom transfer (HAT) processes. Its application potential is exemplified through the implementation of scale-up operations.
{"title":"Dual HATs-mediated Catalyst-free sp3 C-H Bond Functionalization for Regioselective Radical Hydroalkylation of Ynazoles","authors":"Yu-Xin Wu, Xiang Chen, Bang-Yan Ou, Qian Yan, Si-Han Chen, Ya-Wen Zhao, Zhi-Wei Li, Han-Wen Liu, Jiang-Sheng Li","doi":"10.1002/adsc.202401372","DOIUrl":"https://doi.org/10.1002/adsc.202401372","url":null,"abstract":"Direct hydroalkylation of ynazoles, facilitating the efficient synthesis of linear N-β-vinylazoles, is accomplished through the functionalization of sp3 C-H bonds using trace amounts of dioxygen as an initiator. This reagent-free method eliminates the need for exogenous reagents and proceeds through a radical chain mechanism involving dual hydrogen atom transfer (HAT) processes. Its application potential is exemplified through the implementation of scale-up operations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991536","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}
As of 2025, Advanced Synthesis and Catalysis joins the Advanced Portfolio from Wiley. Led by the world-renowned journal Advanced Materials, the Advanced Portfolio is a family of globally respected, high-impact journals that disseminate the best science. With the inclusion of Advanced Synthesis and Catalysis, it is broadening its reach into the field of chemistry. Cover image provided courtesy of Liang Zhao and co-workers from Dalian University of Technology.
{"title":"Front Cover Picture: (Adv. Synth. Catal. 1/2025)","authors":"","doi":"10.1002/adsc.202580101","DOIUrl":"https://doi.org/10.1002/adsc.202580101","url":null,"abstract":"As of 2025, Advanced Synthesis and Catalysis joins the Advanced Portfolio from Wiley. Led by the world-renowned journal Advanced Materials, the Advanced Portfolio is a family of globally respected, high-impact journals that disseminate the best science. With the inclusion of Advanced Synthesis and Catalysis, it is broadening its reach into the field of chemistry. Cover image provided courtesy of Liang Zhao and co-workers from Dalian University of Technology.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"98 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987872","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 general protocol for the efficient synthesis of a variety of highly functionalized pyridin‐4‐ones has been developed through a sequential Wolff rearrangement and [3+3] annulation reaction of enaminones and diazo compounds. This straightforward approach features wide substrate applicability, good substrate tolerance, moderate to excellent yields, and without any catalyst, and enables access to structurally diverse pyridin‐4‐one skeletons. Additionally, scale‐up experiments and synthetic derivatizations demonstrated the potential synthetic utility of the transformations.
{"title":"Catalyst‐free Sequential Wolff Rearrangement and [3+3] Annulation of Enaminones and Diazo compounds Enabling the Assembly of Highly Functionalized Pyridin‐4‐ones","authors":"Yunzheng Wei, Longkun Chen, Huimin Hu, Yu Zhang, Shaolin Yang, Yu Xu, Li Chen, Fuchao Yu","doi":"10.1002/adsc.202401561","DOIUrl":"https://doi.org/10.1002/adsc.202401561","url":null,"abstract":"A general protocol for the efficient synthesis of a variety of highly functionalized pyridin‐4‐ones has been developed through a sequential Wolff rearrangement and [3+3] annulation reaction of enaminones and diazo compounds. This straightforward approach features wide substrate applicability, good substrate tolerance, moderate to excellent yields, and without any catalyst, and enables access to structurally diverse pyridin‐4‐one skeletons. Additionally, scale‐up experiments and synthetic derivatizations demonstrated the potential synthetic utility of the transformations.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"27 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986775","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 1,3‐iodoesterification of 2‐substituted indoles with trihaloacetic acid, iodination reagent, and hypervalent iodine(III) compound was developed as an acid‐promoted C<sub>sp2</sub>–H/C<sub>sp3</sub>–H dual functionalization reaction to furnish 3‐iodo‐2‐trihaloacetoxymethyl indoles. The one‐pot 1,3‐iodoesterification/hydrolysis of the trihaloester group provided 3‐iodo‐2‐pivaloylmethyl indoles via the rearrangement of the pivaloyl group. The reaction proceeded through a trihaloacetic acid‐assisted electrophilic activation of the iodination reagent after the formation of an indolyl(mesityl)iodonium trihaloacetate.
{"title":"1,3‐Iodoesterification of 2‐Substituted Indoles via Csp2–H/Csp3–H Retained Dual Functionalization Using Hypervalent Iodine(III)","authors":"Hiroko Wasaki, Katsuhiko Moriyama","doi":"10.1002/adsc.202401496","DOIUrl":"https://doi.org/10.1002/adsc.202401496","url":null,"abstract":"A 1,3‐iodoesterification of 2‐substituted indoles with trihaloacetic acid, iodination reagent, and hypervalent iodine(III) compound was developed as an acid‐promoted C<sub>sp2</sub>–H/C<sub>sp3</sub>–H dual functionalization reaction to furnish 3‐iodo‐2‐trihaloacetoxymethyl indoles. The one‐pot 1,3‐iodoesterification/hydrolysis of the trihaloester group provided 3‐iodo‐2‐pivaloylmethyl indoles via the rearrangement of the pivaloyl group. The reaction proceeded through a trihaloacetic acid‐assisted electrophilic activation of the iodination reagent after the formation of an indolyl(mesityl)iodonium trihaloacetate.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986777","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}
Yu Xing, Xiangheng Li, Zihan Ni, Jiajian Guo, Zijun Zhou, Lei Cui, Chunju Li, Jian Li
A cascade reaction involving 2‐isocyanophenyl propargylic ester and 4‐hydroxy‐2H‐chromen‐2‐one has been documented. This reaction leads to the formation of a highly strained cyclopropen‐imine species, thereby offering an efficient route to synthesize quinoline‐fused polycyclic skeletons.
{"title":"Formal [3+1+1+1] annulation of 2‐isocyanophenyl propargylic esters and 4‐hydroxy‐2H‐chromen‐2‐ones: an access to quinoline‐fused polycyclic skeletons","authors":"Yu Xing, Xiangheng Li, Zihan Ni, Jiajian Guo, Zijun Zhou, Lei Cui, Chunju Li, Jian Li","doi":"10.1002/adsc.202401462","DOIUrl":"https://doi.org/10.1002/adsc.202401462","url":null,"abstract":"A cascade reaction involving 2‐isocyanophenyl propargylic ester and 4‐hydroxy‐2H‐chromen‐2‐one has been documented. This reaction leads to the formation of a highly strained cyclopropen‐imine species, thereby offering an efficient route to synthesize quinoline‐fused polycyclic skeletons.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"29 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986778","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}
Jun Sun, Yu Wei, Wenjian Wang, Wen Lin, Chaodong Wang, Jiadi Zhou, Guan Wang, Jianjun Li
Herein, we disclose a readily available phenothiazine derivative as an oxidizing organic photocatalyst, that serves to induce radical cascade sulfonylation/cyclization reaction of enaminones. A variety of 3-sulfonyl chromones have been obtained with moderate to excellent yields. This catalytic platform proceeds under metal-free conditions with a wide substrate scope and broad functional group compatibility, which unlocks the new reactivity of phenothiazine derivatives and adds significant synthetic values to <i>O</i>-heterocycles.
{"title":"Organic Photoredox Catalytic Sulfonylation of Enaminones to Access 3-Sulfonyl Chromones","authors":"Jun Sun, Yu Wei, Wenjian Wang, Wen Lin, Chaodong Wang, Jiadi Zhou, Guan Wang, Jianjun Li","doi":"10.1002/adsc.202401396","DOIUrl":"https://doi.org/10.1002/adsc.202401396","url":null,"abstract":"Herein, we disclose a readily available phenothiazine derivative as an oxidizing organic photocatalyst, that serves to induce radical cascade sulfonylation/cyclization reaction of enaminones. A variety of 3-sulfonyl chromones have been obtained with moderate to excellent yields. This catalytic platform proceeds under metal-free conditions with a wide substrate scope and broad functional group compatibility, which unlocks the new reactivity of phenothiazine derivatives and adds significant synthetic values to <i>O</i>-heterocycles.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"41 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988329","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}
Mariur Rodriguez Moreno, Mary L. Setelin, Joshua D. Hansen, James L. Corey, Kirt L. Noble, Lillian R. Stillwell, Emily Angell, Olivia A. Stubbs, Jugal Kumawat, Carlos Santiago Muñoz Gomez, Stacey J. Smith, Daniel H. Ess, David Michaelis
The amination of aryl halides with palladium catalysts (Buchwald‐Hartwig amination) is a widely used transformation in synthetic and drug discovery chemistry. In this report, we demonstrate that a monometallic 2‐phosphinoimidazole Pd catalyst exhibits comparable or enhanced reactivity when compared to all ligands screened for room temperature amination of aryl chlorides with secondary amines. The di‐tert‐butylphosphine derivative showed extremely high reactivity while the di‐isopropyl variant led to almost complete loss of catalytic activity. Computational and experimental mechanistic and kinetic studies indicate that a monometallic Pd structure rather than a bimetallic Pd structure is key to fast catalysis. The di‐tert‐butylphosphine ligand has fast catalysis because it thermodynamically disfavors the formation of a much less active bimetallic Pd complex. A wide substrate scope is demonstrated for the arylation of secondary amines with aryl chlorides using our new catalyst system.
{"title":"Controlling Catalyst Speciation to Achieve Room Temperature Pd‐Catalyzed Aminations with Aryl and Heteroaryl Chlorides","authors":"Mariur Rodriguez Moreno, Mary L. Setelin, Joshua D. Hansen, James L. Corey, Kirt L. Noble, Lillian R. Stillwell, Emily Angell, Olivia A. Stubbs, Jugal Kumawat, Carlos Santiago Muñoz Gomez, Stacey J. Smith, Daniel H. Ess, David Michaelis","doi":"10.1002/adsc.202401337","DOIUrl":"https://doi.org/10.1002/adsc.202401337","url":null,"abstract":"The amination of aryl halides with palladium catalysts (Buchwald‐Hartwig amination) is a widely used transformation in synthetic and drug discovery chemistry. In this report, we demonstrate that a monometallic 2‐phosphinoimidazole Pd catalyst exhibits comparable or enhanced reactivity when compared to all ligands screened for room temperature amination of aryl chlorides with secondary amines. The di‐tert‐butylphosphine derivative showed extremely high reactivity while the di‐isopropyl variant led to almost complete loss of catalytic activity. Computational and experimental mechanistic and kinetic studies indicate that a monometallic Pd structure rather than a bimetallic Pd structure is key to fast catalysis. The di‐tert‐butylphosphine ligand has fast catalysis because it thermodynamically disfavors the formation of a much less active bimetallic Pd complex. A wide substrate scope is demonstrated for the arylation of secondary amines with aryl chlorides using our new catalyst system.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986776","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}
Herein, an iron-catalyzed protocol for the aromatization-driven deconstruction and decarboxylation of ketone-derived dihydroquinazolinones in reaction with unsaturated carboxylic acids is reported. A diverse range of fluoroacrylic acids and cinnamic acids reacted effectively with dihydroquinazolinones, yielding essential monofluoroalkenes and alkenes with excellent stereoselectivity. Additionally, spiro-dihydroquinazolinones served as suitable substrates, facilitating the synthesis of valuable quinazolin-4(3H)-ones featuring alkene motifs. This protocol is notable for its operational simplicity and versatility, enabling the chemical diversification of active molecules.
{"title":"Iron-Catalyzed Decarboxylative and Deconstructive Cross-Coupling of Acrylic Acids with Ketone-Derived Dihydroquinazolinones","authors":"Xiao-Yu Lu, Meng-Xue Su, Hua-Yi Huang, Yu-Jun Qian, Hai-Lun Sun, Xiang Li, Xin-Ru Hu, Hao-Yu Dong","doi":"10.1002/adsc.202401503","DOIUrl":"https://doi.org/10.1002/adsc.202401503","url":null,"abstract":"Herein, an iron-catalyzed protocol for the aromatization-driven deconstruction and decarboxylation of ketone-derived dihydroquinazolinones in reaction with unsaturated carboxylic acids is reported. A diverse range of fluoroacrylic acids and cinnamic acids reacted effectively with dihydroquinazolinones, yielding essential monofluoroalkenes and alkenes with excellent stereoselectivity. Additionally, spiro-dihydroquinazolinones served as suitable substrates, facilitating the synthesis of valuable quinazolin-4(3H)-ones featuring alkene motifs. This protocol is notable for its operational simplicity and versatility, enabling the chemical diversification of active molecules.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"9 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981646","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}
Yasuhiro Yamashita, Tomoya Hisada, Yuki Sato, Shu Kobayashi
Mg(SPh)2 has been found to be a highly active catalyst in photocatalytic alkylation reactions of active methylene compounds with nonactivated alkenes. The desired reactions proceeded smoothly to afford the corresponding alkylated products in high yields with low catalyst loadings (0.2-0.3 mol%). This protocol is applicable to a continuous-flow system. Notably, magnesium is an earth-abundant metal, and Mg(SPh)2 exhibits higher catalytic activity than the previously reported LiSPh.
{"title":"Mg(SPh)2 as a Catalyst for Efficient Photocatalytic Alkylation Reactions of Active Methylene Compounds with Nonactivated Alkenes","authors":"Yasuhiro Yamashita, Tomoya Hisada, Yuki Sato, Shu Kobayashi","doi":"10.1002/adsc.202401554","DOIUrl":"https://doi.org/10.1002/adsc.202401554","url":null,"abstract":"Mg(SPh)2 has been found to be a highly active catalyst in photocatalytic alkylation reactions of active methylene compounds with nonactivated alkenes. The desired reactions proceeded smoothly to afford the corresponding alkylated products in high yields with low catalyst loadings (0.2-0.3 mol%). This protocol is applicable to a continuous-flow system. Notably, magnesium is an earth-abundant metal, and Mg(SPh)2 exhibits higher catalytic activity than the previously reported LiSPh.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981645","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 visible-light-induced intramolecular crossed [2 + 2] cycloaddition reaction of allene-tethered alkylidenecyclopropanes was reported in this paper. The reactions were conducted under mild conditions using Iridium(III) catalyst FirPic as a photosensitizer for energy transfer, affording bridged bicyclic alkenes in moderate to good yields with excellent regioselectivity and stereoselectivity through the regulation of substituents at the olefin’s terminal position. Meanwhile, the computational study explained the special region control assisted by sulfonyl radicals in detail.
{"title":"Intramolecular Crossed [2 + 2] Cycloaddition through Visible-light Triplet Sensitization: Expedient Access to Bridged Bicyclic Alkene","authors":"Min Li, Le-Yi Tao, Xin-Tao Gu, Yin Wei, Min Shi","doi":"10.1002/adsc.202401402","DOIUrl":"https://doi.org/10.1002/adsc.202401402","url":null,"abstract":"A visible-light-induced intramolecular crossed [2 + 2] cycloaddition reaction of allene-tethered alkylidenecyclopropanes was reported in this paper. The reactions were conducted under mild conditions using Iridium(III) catalyst FirPic as a photosensitizer for energy transfer, affording bridged bicyclic alkenes in moderate to good yields with excellent regioselectivity and stereoselectivity through the regulation of substituents at the olefin’s terminal position. Meanwhile, the computational study explained the special region control assisted by sulfonyl radicals in detail.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"84 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981651","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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