Bingning Yan, Qingzhong Zhang, Yifei Ling, jiaxin liu, Jun Yang
IIn this paper, a visible-light-induced intramolecular [2+2] cycloaddition has been revealed to synthesize the bishomocubanone derivatives in moderate to excellent yield under mild conditions. This method demonstrated a broad substrate scope and excellent functional-group tolerance, affording cubane precursors and a series of bishomocubanones. Meanwhile, a hundred-gram scale experiment of this method has been employed to synthesize cubane precursors with 98% yield.
{"title":"Synthesis of bishomocubanone derivatives via visible-light-induced intramolecular [2+2] cycloaddition reaction","authors":"Bingning Yan, Qingzhong Zhang, Yifei Ling, jiaxin liu, Jun Yang","doi":"10.1002/adsc.202401345","DOIUrl":"https://doi.org/10.1002/adsc.202401345","url":null,"abstract":"IIn this paper, a visible-light-induced intramolecular [2+2] cycloaddition has been revealed to synthesize the bishomocubanone derivatives in moderate to excellent yield under mild conditions. This method demonstrated a broad substrate scope and excellent functional-group tolerance, affording cubane precursors and a series of bishomocubanones. Meanwhile, a hundred-gram scale experiment of this method has been employed to synthesize cubane precursors with 98% yield.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"2 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874570","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 and DMAP relay-catalyzed strategy has been achieved for the modular synthesis of 2-alkoxy quinolines from a three-component coupling of terminal alkynes, anthranils, and alcohols. In this protocol, a novel quinoline pyridine salt is formed and serves as a key intermediate in the formation of 2-alkoxy quinolines. The reaction has a broad substrate scope of each reaction partners, affording diversified 2-alkoxy quinoline products in generally good yields.
{"title":"Copper and DMAP relay-catalyzed three-component coupling of terminal alkynes, anthranils and alcohols for the modular synthesis of 2-alkoxy quinolines","authors":"haixia Li, Yang Gao, xiongwei Zhong, Yanping Huo, Xianwei Li, Qian Chen","doi":"10.1002/adsc.202401293","DOIUrl":"https://doi.org/10.1002/adsc.202401293","url":null,"abstract":"A copper and DMAP relay-catalyzed strategy has been achieved for the modular synthesis of 2-alkoxy quinolines from a three-component coupling of terminal alkynes, anthranils, and alcohols. In this protocol, a novel quinoline pyridine salt is formed and serves as a key intermediate in the formation of 2-alkoxy quinolines. The reaction has a broad substrate scope of each reaction partners, affording diversified 2-alkoxy quinoline products in generally good yields.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874308","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}
Takeshi Hata, Koki Nishi, Koki Yamaguchi, Yuta Tatsumi, Naomi Tanaka, Masayuki Shigeta, Hirokazu Urabe
This study aims to develop a more efficient, functional-group-tolerant approach using stable nitroalkanes and reductive coupling reactions with aliphatic Grignard/cerium and organozinc reagents. The treatment of nitroalkanes with aliphatic Grignard reagents in the presence of a catalytic amount of CuF<sub>2</sub> and stoichiometric amount of CeCl<sub>3</sub> affords various nitrones in good yields as single isomers. The reaction of tertiary nitroalkanes with organozinc reagents affords various functionalized nitrones without CuF<sub>2</sub> or CeCl<sub>3</sub>. These reductive coupling reactions proceed without the loss of functional groups such as alkene, alkyne, benzyl ether, chlorine, ester, and nitrile moieties. Nitrones can also be used as precursors for [3+2] cyclizations with electron-withdrawing alkenes and alkynes.
{"title":"Copper-Catalyzed Reductive Coupling of Nitroalkanes with Aliphatic Grignard/Cerium and Organozinc Reagents for Synthesis of Functionalized Nitrones","authors":"Takeshi Hata, Koki Nishi, Koki Yamaguchi, Yuta Tatsumi, Naomi Tanaka, Masayuki Shigeta, Hirokazu Urabe","doi":"10.1002/adsc.202401259","DOIUrl":"https://doi.org/10.1002/adsc.202401259","url":null,"abstract":"This study aims to develop a more efficient, functional-group-tolerant approach using stable nitroalkanes and reductive coupling reactions with aliphatic Grignard/cerium and organozinc reagents. The treatment of nitroalkanes with aliphatic Grignard reagents in the presence of a catalytic amount of CuF<sub>2</sub> and stoichiometric amount of CeCl<sub>3</sub> affords various nitrones in good yields as single isomers. The reaction of tertiary nitroalkanes with organozinc reagents affords various functionalized nitrones without CuF<sub>2</sub> or CeCl<sub>3</sub>. These reductive coupling reactions proceed without the loss of functional groups such as alkene, alkyne, benzyl ether, chlorine, ester, and nitrile moieties. Nitrones can also be used as precursors for [3+2] cyclizations with electron-withdrawing alkenes and alkynes.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"26 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874316","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}
Here, we present an innovative approach to achieve Minisci-type alkylation of cyclic N-ketimines, enabling access to a diverse range of valuable alkylated sulfonyl ketimines via iron hydride hydrogen atom transfer. More than 35 examples are shown with a wide range of substrates. Additionally, this system is easy to operate and can be efficiently scaled up. Mechanistic investigations revealed that the alkyl radical process involved and the air acts as the sole oxidant in this system.
{"title":"Iron Catalyzed Radical Alkylation of Cyclic Ketimines with olefins via Metal Hydride Atom Transfer","authors":"Xixi Hu, Ruizhi Sun, Yu Tian, Xinyue Xu, Yijia Zhu, Hui Liu, Dong Liu, Lizhi Zhang","doi":"10.1002/adsc.202401430","DOIUrl":"https://doi.org/10.1002/adsc.202401430","url":null,"abstract":"Here, we present an innovative approach to achieve Minisci-type alkylation of cyclic N-ketimines, enabling access to a diverse range of valuable alkylated sulfonyl ketimines via iron hydride hydrogen atom transfer. More than 35 examples are shown with a wide range of substrates. Additionally, this system is easy to operate and can be efficiently scaled up. Mechanistic investigations revealed that the alkyl radical process involved and the air acts as the sole oxidant in this system.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"1 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874258","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}
Jorge Sanz-Garrido, Román Andrés, Camino González-Arellano, Juan C. Flores
A half-sandwich nickel complex containing an NHC-carboxylate chelate ligand (i.e., [Ni(η5-Cp)(κ2-C,O-NHC)]) derived from the (S)-leucine has been identified for the selective hydrothiolation of terminal acetylenes toward challenging Markovnikov-type 𝛼 vinyl thioethers, even with aryl alkynes. The activity and selectivity exhibited by the nickel complex are comparable, if not superior, to those of complexes of rhodium reported to be the best catalysts to date for the Markovnikov addition in the thiol-yne reaction. The experimental data are consistent with the participation of the coordinated carboxylate group in the catalytic reaction as an intermolecular acid-base co-catalyst, favoring the formation of nickel-thiolate intermediates.
{"title":"Regioselective hydrothiolation of terminal alkynes using half-sandwich Ni(II) catalysts bearing bidentate NHC-carboxylate ligands.","authors":"Jorge Sanz-Garrido, Román Andrés, Camino González-Arellano, Juan C. Flores","doi":"10.1002/adsc.202401289","DOIUrl":"https://doi.org/10.1002/adsc.202401289","url":null,"abstract":"A half-sandwich nickel complex containing an NHC-carboxylate chelate ligand (i.e., [Ni(η5-Cp)(κ2-C,O-NHC)]) derived from the (S)-leucine has been identified for the selective hydrothiolation of terminal acetylenes toward challenging Markovnikov-type 𝛼 vinyl thioethers, even with aryl alkynes. The activity and selectivity exhibited by the nickel complex are comparable, if not superior, to those of complexes of rhodium reported to be the best catalysts to date for the Markovnikov addition in the thiol-yne reaction. The experimental data are consistent with the participation of the coordinated carboxylate group in the catalytic reaction as an intermolecular acid-base co-catalyst, favoring the formation of nickel-thiolate intermediates.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"43 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874307","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 variety of structurally diverse spirocyclohexane oxindoles featuring a quaternary carbon centre have been successfully constructed through an N‐heterocyclic carbene‐catalyzed [4+2] annulation of isatin‐derived enals with α cyano‐β‐methylenones. This domino process exhibits a wide substrate tolerance, operates under mild conditions, and yields products with high enantioselectivity.
{"title":"N‐Heterocyclic Carbene‐Catalyzed Enantioselective Synthesis of Spirocyclohexane Oxindoles","authors":"Ye Zhang, Zhoulu Wang, Min Ren, Zhenqian Fu","doi":"10.1002/adsc.202401205","DOIUrl":"https://doi.org/10.1002/adsc.202401205","url":null,"abstract":"A variety of structurally diverse spirocyclohexane oxindoles featuring a quaternary carbon centre have been successfully constructed through an N‐heterocyclic carbene‐catalyzed [4+2] annulation of isatin‐derived enals with α cyano‐β‐methylenones. This domino process exhibits a wide substrate tolerance, operates under mild conditions, and yields products with high enantioselectivity.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832611","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 new strategy for the construction of chiral 4H‐chromene skeleton via Pd‐catalyzed asymmetric amination of 2H‐chromene was reported. A series of chiral 2‐trifluoromethyl‐4H‐chromenes containing 1,2,3,4‐tetrahydroquinoline unit were synthesized in moderate to good yields with excellent enantioselectivity, the method serves as an effective supplement to the construction of chiral 4H‐chromene skeleton.
{"title":"Synthesis of chiral 2‐trifluoromethyl‐4‐(tetrahydroquinolinyl)‐4H‐chromenes via Pd‐catalyzed asymmetric amination","authors":"Bang Zhong Wang, Luyang Sun, Pengyue Zhang, Shuaibo Zhang, Jinfeng Zhao, Jingping Qu, Yuhan Zhou","doi":"10.1002/adsc.202401422","DOIUrl":"https://doi.org/10.1002/adsc.202401422","url":null,"abstract":"A new strategy for the construction of chiral 4H‐chromene skeleton via Pd‐catalyzed asymmetric amination of 2H‐chromene was reported. A series of chiral 2‐trifluoromethyl‐4H‐chromenes containing 1,2,3,4‐tetrahydroquinoline unit were synthesized in moderate to good yields with excellent enantioselectivity, the method serves as an effective supplement to the construction of chiral 4H‐chromene skeleton.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"144 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832627","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, we report a conceptually new, general, and efficient approach for the synthesis of valuable ortho‐azido‐1,5‐disubstituted tetrazole and one‐pot synthesis of ortho‐triazoletetrazole derivatives mainly via PIDA mediated N‐N cleavage of the azole ring of 2H‐indazoles using TMSN3. This current methodology represents an array of unsymmetrical ortho‐azidotetrazole and ortho‐triazoletetrazole derivatives with wide functional group tolerance in good to excellent yields under mild reaction conditions. The practical utility of this reaction was showcased through successful scale‐up synthesis and a variety of subsequent derivatizations of ortho‐azidotetrazole products. Mechanistic investigations indicate that the reaction proceeds through a radical pathway.
{"title":"Diverse Synthesis of Azoles: Construction of ortho‐Azidotetrazoles/Triazoletetrazoles through N‐N Cleavage of 2H‐Indazoles","authors":"Sudip Laru, Suvam Bhattacharjee, Alakananda Hajra","doi":"10.1002/adsc.202401423","DOIUrl":"https://doi.org/10.1002/adsc.202401423","url":null,"abstract":"Herein, we report a conceptually new, general, and efficient approach for the synthesis of valuable ortho‐azido‐1,5‐disubstituted tetrazole and one‐pot synthesis of ortho‐triazoletetrazole derivatives mainly via PIDA mediated N‐N cleavage of the azole ring of 2H‐indazoles using TMSN3. This current methodology represents an array of unsymmetrical ortho‐azidotetrazole and ortho‐triazoletetrazole derivatives with wide functional group tolerance in good to excellent yields under mild reaction conditions. The practical utility of this reaction was showcased through successful scale‐up synthesis and a variety of subsequent derivatizations of ortho‐azidotetrazole products. Mechanistic investigations indicate that the reaction proceeds through a radical pathway.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"47 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832628","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}
Rajesh T. Bhawale, Abhinay S. Chillal, Umesh A. Kshirsagar
Visible light-induced site-selective C−H alkylation and alkenylation of 2-aryl heteroarenes with maleimides at room temperature via dual catalysis in an aqueous medium has been disclosed. This operationally simple and mild approach enables the selective formation of alkylation and alkenylation products up to 92% yield under silver-free conditions with excellent substrate scope. For the mechanistic examination, KIE, H/D labeling experiments, light on-off experiments, and quantum yield measurements were carried out. Moreover, the present approach for the alkylation and alkenylation of 2-aryl heteroarenes is suitable for scalable synthesis.
{"title":"Visible-Light-Enabled Regioselective C−H alkylation and alkenylation of 2-Aryl Heterocycles using Dual Catalysis","authors":"Rajesh T. Bhawale, Abhinay S. Chillal, Umesh A. Kshirsagar","doi":"10.1002/adsc.202401294","DOIUrl":"https://doi.org/10.1002/adsc.202401294","url":null,"abstract":"<p>Visible light-induced site-selective C−H alkylation and alkenylation of 2-aryl heteroarenes with maleimides at room temperature via dual catalysis in an aqueous medium has been disclosed. This operationally simple and mild approach enables the selective formation of alkylation and alkenylation products up to 92% yield under silver-free conditions with excellent substrate scope. For the mechanistic examination, KIE, H/D labeling experiments, light on-off experiments, and quantum yield measurements were carried out. Moreover, the present approach for the alkylation and alkenylation of 2-aryl heteroarenes is suitable for scalable synthesis.</p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"30 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841634","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}
Dominika Kobus-Bartoszewicz, Mariusz Zalewski, Krzysztof Melcer, Mikołaj Warda, Sebastian Stecko
Herein, we disclose a new photochemical process to prepare γ‐amino acids from allylamines and formic acid salts. The investigated redox‐neutral hydrocarboxylation process produces high yields across a wide range of functionalized allylamine substrates with excellent regioselectivity. The developed operationally simple protocol can be readily scaled with low photocatalyst loading (from 1% up to 0.02 mol%) without the need for any precautions to exclude air or moisture. The mechanistic working model utilizes a thiol‐catalyzed radical chain process, delivering the hydrogen atom and CO2 from formic acid salt across the alkene substrate through the carboxylate radical (CO2•‐), a crucial reactive intermediate.
{"title":"Photoinduced metal‐free hydrocarboxylation of allylamines","authors":"Dominika Kobus-Bartoszewicz, Mariusz Zalewski, Krzysztof Melcer, Mikołaj Warda, Sebastian Stecko","doi":"10.1002/adsc.202401326","DOIUrl":"https://doi.org/10.1002/adsc.202401326","url":null,"abstract":"Herein, we disclose a new photochemical process to prepare γ‐amino acids from allylamines and formic acid salts. The investigated redox‐neutral hydrocarboxylation process produces high yields across a wide range of functionalized allylamine substrates with excellent regioselectivity. The developed operationally simple protocol can be readily scaled with low photocatalyst loading (from 1% up to 0.02 mol%) without the need for any precautions to exclude air or moisture. The mechanistic working model utilizes a thiol‐catalyzed radical chain process, delivering the hydrogen atom and CO2 from formic acid salt across the alkene substrate through the carboxylate radical (CO2•‐), a crucial reactive intermediate.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"50 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815791","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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