Sophi R. Todtz, Soumik Das, Paul M. Zimmerman, James J. Devery
A challenge for the acid-mediated formation of oxabicyclo[3.3.1]nonenes is side product formation. Presented herein is a Lewis acid-catalyzed method towards these structures from aldehydes and α-pinene, forming the endo diastereomer exclusively. We include a proposal for the stereochemical reassignment of previously reported exo diastereomers supported by density functional theory (DFT) calculations, 1H NMR, and X-ray crystallography. The reactive system includes a range of aldehyde substrates. Experimental observations along with quantum chemical simulations suggest that an Fe(III)-aldehyde aggregate functions as the active catalyst.
{"title":"Diastereoselective Synthesis of Oxabicyclo[3.3.1]nonenes from Aldehydes and α-Pinene: Fe(III) Aggregate Catalysis","authors":"Sophi R. Todtz, Soumik Das, Paul M. Zimmerman, James J. Devery","doi":"10.1002/adsc.202401329","DOIUrl":"https://doi.org/10.1002/adsc.202401329","url":null,"abstract":"A challenge for the acid-mediated formation of oxabicyclo[3.3.1]nonenes is side product formation. Presented herein is a Lewis acid-catalyzed method towards these structures from aldehydes and α-pinene, forming the endo diastereomer exclusively. We include a proposal for the stereochemical reassignment of previously reported exo diastereomers supported by density functional theory (DFT) calculations, 1H NMR, and X-ray crystallography. The reactive system includes a range of aldehyde substrates. Experimental observations along with quantum chemical simulations suggest that an Fe(III)-aldehyde aggregate functions as the active catalyst.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"11 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518289","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}
Spirocyclic compounds, particularly spirocyclohexadienones, are important in pharmaceuticals due to their biological activity. In this study, we develop a catalytic cascade oxidative spirocyclization of diarylamines for the rapid access to highly functionalized spirocyclohexadienones. Using commercially available recyclable heterogeneous metal catalysts, cascade process via oxidative coupling and dearomative spiroannulation proceeds efficiently under mild aerobic conditions, providing spirocyclohexadienones fused with an acridine skeleton in good-to-excellent yields. This method provides efficient and rapid access to nitrogen-containing fused spiro compounds in a highly atom-economical and environmentally friendly manner.
{"title":"Heterogeneously Catalyzed Cascade Oxidative Coupling/Dearomative Spirocyclization of Diarylamines: Facile Access to Spiroacridines","authors":"Kenji Matsumoto, Naho Sato, Yoshinori Kobayashi, Kanako Date, Yasuko Okamoto, Touya Kariya, Tsukasa Hirokane, Masahiro Yoshida","doi":"10.1002/adsc.202500107","DOIUrl":"https://doi.org/10.1002/adsc.202500107","url":null,"abstract":"Spirocyclic compounds, particularly spirocyclohexadienones, are important in pharmaceuticals due to their biological activity. In this study, we develop a catalytic cascade oxidative spirocyclization of diarylamines for the rapid access to highly functionalized spirocyclohexadienones. Using commercially available recyclable heterogeneous metal catalysts, cascade process via oxidative coupling and dearomative spiroannulation proceeds efficiently under mild aerobic conditions, providing spirocyclohexadienones fused with an acridine skeleton in good-to-excellent yields. This method provides efficient and rapid access to nitrogen-containing fused spiro compounds in a highly atom-economical and environmentally friendly manner.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"36 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518292","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}
Kai Zheng, Zhaoyang Wang, Yacong Wang, Chao Chen, Chao Shen
The first example for photo-induced oxidative C-H esterification of quinoxalinones with arylaldehydes under benign conditions has been reported. This method is distinguished by its capacity to accommodate a diverse array of quinoxalinones and arylaldehydes, culminating in the synthesis of the corresponding esters with moderate to good yields. The protocol is lauded for its environmental benignity, eschewing the need for hazardous transition metals and costly photocatalysts, and relies solely on hydrogen peroxide (H2O2) as the oxidant. Moreover, the scalability of the synthesis and the derivative transformations of the products have been demonstrated, underscoring its practical utility in organic synthesis.
{"title":"Photo-Induced Oxidative C-H Esterification of Quinoxalinones with Arylaldehydes under Mild Conditions","authors":"Kai Zheng, Zhaoyang Wang, Yacong Wang, Chao Chen, Chao Shen","doi":"10.1002/adsc.202500018","DOIUrl":"https://doi.org/10.1002/adsc.202500018","url":null,"abstract":"The first example for photo-induced oxidative C-H esterification of quinoxalinones with arylaldehydes under benign conditions has been reported. This method is distinguished by its capacity to accommodate a diverse array of quinoxalinones and arylaldehydes, culminating in the synthesis of the corresponding esters with moderate to good yields. The protocol is lauded for its environmental benignity, eschewing the need for hazardous transition metals and costly photocatalysts, and relies solely on hydrogen peroxide (H2O2) as the oxidant. Moreover, the scalability of the synthesis and the derivative transformations of the products have been demonstrated, underscoring its practical utility in organic synthesis.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"72 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526511","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. 4/2025)","authors":"","doi":"10.1002/adsc.202580401","DOIUrl":"https://doi.org/10.1002/adsc.202580401","url":null,"abstract":"<p>As of 2025, Advanced Synthesis and Catalysis joins the \u0000Advanced 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.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"367 4","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/adsc.202580401","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143497066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract. A practical and highly efficient radical 1,3-thiosulfonylation of allylboron esters and allylketones with thiosulfonates via 1,2-functional group migration is described, affording diverse 1,3-thiosulfonylated products in good yields. Notably, this method can be performed under photocatalyst-, base- and additive-free conditions, which features operational simplicity, high atom-economy, excellent functional group tolerance and versatile transformations of the products.
{"title":"Photocatalyst-, Base- and Additive-Free, Visible-Light Induced 1,3-Thiosulfonylation of Allylboronic Esters and Allylketones with Thiosulfonates","authors":"Xin Zheng, Tuanli Yao, Kaiping Wang, Guodong Zhang, shuilong zhang, Xiang Li","doi":"10.1002/adsc.202500051","DOIUrl":"https://doi.org/10.1002/adsc.202500051","url":null,"abstract":"Abstract. A practical and highly efficient radical 1,3-thiosulfonylation of allylboron esters and allylketones with thiosulfonates via 1,2-functional group migration is described, affording diverse 1,3-thiosulfonylated products in good yields. Notably, this method can be performed under photocatalyst-, base- and additive-free conditions, which features operational simplicity, high atom-economy, excellent functional group tolerance and versatile transformations of the products.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"7 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518337","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}
We report a collection of “selectivity rules” for the dearomative (3+2) annulation reaction between substituted indoles and oxyallyl cations. The application of these rules enables us to synthesize four different regioisomeric permutations of the annulation products in a stereoselective fashion. We demonstrated that these products could be further transformed into hexahydro- and tetrahydrocarbazoles by nucleophile-intercepted Beckmann fragmentation (NuBFr) and Beckmann fragmentation (BFr).
{"title":"Selectivity Rules for the Dearomative (3+2) Annulation Reaction Between Substituted Indoles and Oxyallyl Cations","authors":"Dhiman Saha, Jimmy Wu","doi":"10.1002/adsc.202401536","DOIUrl":"https://doi.org/10.1002/adsc.202401536","url":null,"abstract":"We report a collection of “selectivity rules” for the dearomative (3+2) annulation reaction between substituted indoles and oxyallyl cations. The application of these rules enables us to synthesize four different regioisomeric permutations of the annulation products in a stereoselective fashion. We demonstrated that these products could be further transformed into hexahydro- and tetrahydrocarbazoles by nucleophile-intercepted Beckmann fragmentation (NuBFr) and Beckmann fragmentation (BFr).","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"44 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518299","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}
Abstract. The demonstrated light-initiated addition of radicals formed on an active methylene group to styrene derivatives exhibits a product selectivity influenced by the presence of a protic solvent. Under protic conditions, the predominant products are branched compounds with the alkene moiety attached to the methylene group. In the absence of a proton source, an alkene is incorporated between the carbonyl group and the methylene group, forming products known from the De Mayo reaction. The utility of the presented method was confirmed by a broad substrate range of alkenes and compounds bearing active methylene groups. A comprehensive mechanistic study revealed that both types of products can be formed via the radical pathway. This suggests a previously unreported mechanistic path as an alternative to the De Mayo reaction, which gives the same type of products.
{"title":"Double-sided control of product type preference in the visible-light initiated reaction of 1,3-dicarbonyl compounds with alkenes","authors":"Małgorzata Pałyga, Jan Rzepiela, Sebastian Baś","doi":"10.1002/adsc.202500009","DOIUrl":"https://doi.org/10.1002/adsc.202500009","url":null,"abstract":"Abstract. The demonstrated light-initiated addition of radicals formed on an active methylene group to styrene derivatives exhibits a product selectivity influenced by the presence of a protic solvent. Under protic conditions, the predominant products are branched compounds with the alkene moiety attached to the methylene group. In the absence of a proton source, an alkene is incorporated between the carbonyl group and the methylene group, forming products known from the De Mayo reaction. The utility of the presented method was confirmed by a broad substrate range of alkenes and compounds bearing active methylene groups. A comprehensive mechanistic study revealed that both types of products can be formed via the radical pathway. This suggests a previously unreported mechanistic path as an alternative to the De Mayo reaction, which gives the same type of products.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"32 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495756","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}
Catalytic formal aldol condensation reactions between β-ketophosphonates and arylaldehydes, in which the C-C double bond formation occurs at the γ-position of the β-ketophosphonate, are reported. The reactions were performed in the presence of a catalyst system composed of <i>p</i>-anisidine and trifluoroacetic acid under mild conditions. Mechanistic investigations suggest that a Mannich reaction followed by elimination results in the formation of the γ,δ-unsaturated β-ketophosphonate. Although the β-ketophosphonate has an active methylene group, the bond formation occurred selectively at the γ-position of the β-ketophosphonate.
{"title":"Catalytic γ-Position-Selective Reactions of (2-Oxopropyl)phosphonates with Aldehydes to Afford γ,δ-Unsaturated β-Ketophosphonates","authors":"James Osborne, Fujie Tanaka","doi":"10.1002/adsc.202401375","DOIUrl":"https://doi.org/10.1002/adsc.202401375","url":null,"abstract":"Catalytic formal aldol condensation reactions between β-ketophosphonates and arylaldehydes, in which the C-C double bond formation occurs at the γ-position of the β-ketophosphonate, are reported. The reactions were performed in the presence of a catalyst system composed of <i>p</i>-anisidine and trifluoroacetic acid under mild conditions. Mechanistic investigations suggest that a Mannich reaction followed by elimination results in the formation of the γ,δ-unsaturated β-ketophosphonate. Although the β-ketophosphonate has an active methylene group, the bond formation occurred selectively at the γ-position of the β-ketophosphonate.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"51 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495757","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}
Karthik Rajan Rajamanickam, Minwoo Park, Kyungho Park, Sunwoo Lee
A sustainable photochemical reductive transamidation of nitroarenes catalyzed by FeCl3 under blue LED irradiation is reported. This method eliminates the need for pre-reduction steps or stoichiometric reducing agents by utilizing sacrificial C-H bonds from organic solvents. The reaction proceeds via FeCl3-catalyzed single-electron transfer (SET) and hydrogen atom transfer (HAT) cascades. A previously unreported intermediate formed between nitroarenes and N-methylpyrrolidone (NMP) is discovered, playing a crucial role in facilitating substitution with amides. The method exhibits broad functional group tolerance and achieves yields up to 82%, demonstrating compatibility with a wide range of nitroarenes and amides.
{"title":"FeCl3-Catalyzed Photochemical Reductive Transamidation of Nitroarenes: A Sustainable Approach Using Sacrificial C–H Bonds","authors":"Karthik Rajan Rajamanickam, Minwoo Park, Kyungho Park, Sunwoo Lee","doi":"10.1002/adsc.202401574","DOIUrl":"https://doi.org/10.1002/adsc.202401574","url":null,"abstract":"A sustainable photochemical reductive transamidation of nitroarenes catalyzed by FeCl3 under blue LED irradiation is reported. This method eliminates the need for pre-reduction steps or stoichiometric reducing agents by utilizing sacrificial C-H bonds from organic solvents. The reaction proceeds via FeCl3-catalyzed single-electron transfer (SET) and hydrogen atom transfer (HAT) cascades. A previously unreported intermediate formed between nitroarenes and N-methylpyrrolidone (NMP) is discovered, playing a crucial role in facilitating substitution with amides. The method exhibits broad functional group tolerance and achieves yields up to 82%, demonstrating compatibility with a wide range of nitroarenes and amides.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495552","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}
We report a photoredox assisted α-acylation of enol acetates with acyl chlorides using catalytic amount of Ir(ppy)3. The reaction proceeds via net-redox neutral radical-polar crossover pathway and furnishes 1,3-diketones in moderate to high yields under mild conditions without an external oxidant. The application of this method is demonstrated in the synthesis of Avobenzone (main ingredient in sunscreens), one-pot synthesis of anti-bacterial 4H-1,4-benzothiazines and organic-laser dye boron difluoride hemicurcuminoid complex.
{"title":"Photoredox assisted net-neutral radical-polar crossover α-acylation of enol acetates with acyl chlorides: Access to 1,3-diketones","authors":"Rohit Kumar, Harsha Harsha, Nidhi Jain","doi":"10.1002/adsc.202500007","DOIUrl":"https://doi.org/10.1002/adsc.202500007","url":null,"abstract":"We report a photoredox assisted α-acylation of enol acetates with acyl chlorides using catalytic amount of Ir(ppy)3. The reaction proceeds via net-redox neutral radical-polar crossover pathway and furnishes 1,3-diketones in moderate to high yields under mild conditions without an external oxidant. The application of this method is demonstrated in the synthesis of Avobenzone (main ingredient in sunscreens), one-pot synthesis of anti-bacterial 4H-1,4-benzothiazines and organic-laser dye boron difluoride hemicurcuminoid complex.","PeriodicalId":118,"journal":{"name":"Advanced Synthesis & Catalysis","volume":"22 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486416","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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