Changhee Park, Seyun Gi, Seongkyeong Yoon, Seong Jung Kwon, Sunggi Lee
Amine carboxyborane enabled an efficient halogen atom transfer (XAT) with 1o, 2o, and 3o alkyl bromides, resulting in Giese addition products with various electron-deficient double bonds. Moreover, direct addition of several boryl radicals was also possible using several ligated carboxyboranes.
{"title":"Giese Reaction of Alkyl Bromides using Amine Carboxyboranes","authors":"Changhee Park, Seyun Gi, Seongkyeong Yoon, Seong Jung Kwon, Sunggi Lee","doi":"10.1039/d4qo02325k","DOIUrl":"https://doi.org/10.1039/d4qo02325k","url":null,"abstract":"Amine carboxyborane enabled an efficient halogen atom transfer (XAT) with 1<small><sup>o</sup></small>, 2<small><sup>o</sup></small>, and 3<small><sup>o</sup></small> alkyl bromides, resulting in Giese addition products with various electron-deficient double bonds. Moreover, direct addition of several boryl radicals was also possible using several ligated carboxyboranes.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"39 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kang Lv, Yihang Zhou, Zitong Meng, Jing Zhang, Tao Liu
Density functional theory (DFT) calculations were performed to study Pd-catalyzed ipso,meta-dimethylation reaction of ortho-substituted iodoarenes. In the presence of K2CO3, aryl−I oxidative addition on Pd(0) catalysts can generate arylpalladium(II) intermediate, which undergoes two sequent processes of C−H activation, CH3−I oxidative addition (Ar−C reductive elimination/CH3−I oxidative addition/Ar−C oxidative addition), and Ar−C reductive elimination to generate dimethylated intermediate. Then hydrogen transfer, C−hydride reductive elimination, and ligand exchange can take place to generate 2,6-dimethylanisole 3b. With KOAc as the base, 2,3-dihydrobenzofuran 4b can be obtained via aryl−I oxidative addition, two sequent processes of C−H activation/Ar−C reductive elimination/CH3−I oxidative addition/Ar−C oxidative addition/Ar−C reductive elimination, the third C−H activation, reductive elimination, and ligand exchange, respectively. The competition between the third C−H activation and the hydrogen transfer from dimethylated intermediate determines the selectivity of the reaction. The hydrogen transfer is generally superior to the third C−H activation due to the stronger reactivity of methyl group in methanol than normal methyl group. When K2CO3 is used, such electronic effect is dominant. However, when KOAc is employed, different structure and properties with K2CO3 cause the ligand exchange step highly endergonic, thereby rendering subsequent hydrogen transfer not favorable and leading to 2,3-dihydrobenzofuran 4b to be the final product.
{"title":"Computational Study on Pd-Catalyzed ipso,meta-Dimethylation of ortho-Substituted Iodoarene: Mechanisms and the Role of Base","authors":"Kang Lv, Yihang Zhou, Zitong Meng, Jing Zhang, Tao Liu","doi":"10.1039/d4qo02168a","DOIUrl":"https://doi.org/10.1039/d4qo02168a","url":null,"abstract":"Density functional theory (DFT) calculations were performed to study Pd-catalyzed ipso,meta-dimethylation reaction of ortho-substituted iodoarenes. In the presence of K2CO3, aryl−I oxidative addition on Pd(0) catalysts can generate arylpalladium(II) intermediate, which undergoes two sequent processes of C−H activation, CH3−I oxidative addition (Ar−C reductive elimination/CH3−I oxidative addition/Ar−C oxidative addition), and Ar−C reductive elimination to generate dimethylated intermediate. Then hydrogen transfer, C−hydride reductive elimination, and ligand exchange can take place to generate 2,6-dimethylanisole 3b. With KOAc as the base, 2,3-dihydrobenzofuran 4b can be obtained via aryl−I oxidative addition, two sequent processes of C−H activation/Ar−C reductive elimination/CH3−I oxidative addition/Ar−C oxidative addition/Ar−C reductive elimination, the third C−H activation, reductive elimination, and ligand exchange, respectively. The competition between the third C−H activation and the hydrogen transfer from dimethylated intermediate determines the selectivity of the reaction. The hydrogen transfer is generally superior to the third C−H activation due to the stronger reactivity of methyl group in methanol than normal methyl group. When K2CO3 is used, such electronic effect is dominant. However, when KOAc is employed, different structure and properties with K2CO3 cause the ligand exchange step highly endergonic, thereby rendering subsequent hydrogen transfer not favorable and leading to 2,3-dihydrobenzofuran 4b to be the final product.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Qi Xue, Zheng-Li Fu, Wen-Yu Zhang, Xia-Lu Cheng, Yang Li, Hu Cai, Jin-Heng Li
Herein we report a novel palladium-catalyzed intermolecular dearomative [4+2] cycloaddition of 1, 4-enynes with CO and arylamines. Compared with the well-known Himbert intramolecular arene/allene cycloaddtion, this method provides a facile platform for the synthesis of polycyclic γ-lactams, through the formation of four new chemical bonds (three C-C bonds and one C-N bond) in single step, with excellent functional-group tolerance and high atom-economy.
{"title":"Palladium-Catalyzed Multicomponent [4+2] Cycloaddtion of 1, 4-Enynes with CO and Arylamines to Access Polycyclic γ-Lactams via Dearomative Rearrangement","authors":"Qi Xue, Zheng-Li Fu, Wen-Yu Zhang, Xia-Lu Cheng, Yang Li, Hu Cai, Jin-Heng Li","doi":"10.1039/d4qo02304h","DOIUrl":"https://doi.org/10.1039/d4qo02304h","url":null,"abstract":"Herein we report a novel palladium-catalyzed intermolecular dearomative [4+2] cycloaddition of 1, 4-enynes with CO and arylamines. Compared with the well-known Himbert intramolecular arene/allene cycloaddtion, this method provides a facile platform for the synthesis of polycyclic γ-lactams, through the formation of four new chemical bonds (three C-C bonds and one C-N bond) in single step, with excellent functional-group tolerance and high atom-economy.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"50 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Li Li, Yuan-Yang Li, Beibei Li, Linlin Shi, Beiling Gao, Guang-Jian Mei
Chiral bicyclic ureas are important multi-nitrogen-containing polycyclic frameworks and valuable building blocks in organic synthesis. Although many racemic synthetic methods have been reported, their catalytic asymmetric synthesis remains challenging and elusive. Herein, we report the azocarboxamide-enabled enantioselective 1,2-diamination of α‑branched cyclic ketones. Under mild conditions, a wide range of fused bicyclic ureas bearing vicinal N-containing quaternary stereocenters have been prepared in good yield with excellent enantioselectivity. Notably, when α‑carbethoxy cyclic ketones are used as substrates, the reaction proceeds in a cascade of 1,2-diaminization/lactonization, which leads to the formation of highly crowded and structurally unique bridged bicyclic ureas.
{"title":"Access to (Bridged) Bicyclic Ureas through Azocarboxamide-Enabled Enantioselective 1,2-Diamination of α-Branched Cyclic Ketones","authors":"Li Li, Yuan-Yang Li, Beibei Li, Linlin Shi, Beiling Gao, Guang-Jian Mei","doi":"10.1039/d4qo02318h","DOIUrl":"https://doi.org/10.1039/d4qo02318h","url":null,"abstract":"Chiral bicyclic ureas are important multi-nitrogen-containing polycyclic frameworks and valuable building blocks in organic synthesis. Although many racemic synthetic methods have been reported, their catalytic asymmetric synthesis remains challenging and elusive. Herein, we report the azocarboxamide-enabled enantioselective 1,2-diamination of α‑branched cyclic ketones. Under mild conditions, a wide range of fused bicyclic ureas bearing vicinal N-containing quaternary stereocenters have been prepared in good yield with excellent enantioselectivity. Notably, when α‑carbethoxy cyclic ketones are used as substrates, the reaction proceeds in a cascade of 1,2-diaminization/lactonization, which leads to the formation of highly crowded and structurally unique bridged bicyclic ureas.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, we report on a C-H functionalization of 1,3-dicarbonyl compounds via a photocatalytic nitrene transfer reaction. A wide range of 1,3-dicarbonyl substrates and iodinanes were found compatible with the reaction conditions to directly afford the C-H functionalization products without the need of preformation of nucleophilic enolate equivalents. Additionally, a comprehensive series of synthetic applications and control experiments were conducted, thereby further extending the practical utility of this approach.
{"title":"Intermolecular amination of Ethyl Benzo ylacetate via photocatalytic nitrene transfer reactions","authors":"Yujing Guo, Rene M Koenigs, Xin-Qi Hao, Linlin Shi, Yifan Guo, Luyao Ding","doi":"10.1039/d4qo02194k","DOIUrl":"https://doi.org/10.1039/d4qo02194k","url":null,"abstract":"In this study, we report on a C-H functionalization of 1,3-dicarbonyl compounds via a photocatalytic nitrene transfer reaction. A wide range of 1,3-dicarbonyl substrates and iodinanes were found compatible with the reaction conditions to directly afford the C-H functionalization products without the need of preformation of nucleophilic enolate equivalents. Additionally, a comprehensive series of synthetic applications and control experiments were conducted, thereby further extending the practical utility of this approach.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A Rh(III)-catalyzed dearomative 2,3-diamination of indoles with N-alkoxyamides has been developed. The method provides an efficient approach to access 2-(N-acylimino)-3-aminoindolines with high regioselectivity.
{"title":"Dearomative 2,3-Diamination of Indoles Triggered by Rh(III)-Catalyzed Csp2-H Activation","authors":"Cheng-Jie Wang, Huanfeng Jiang, Wei Zeng","doi":"10.1039/d4qo02017k","DOIUrl":"https://doi.org/10.1039/d4qo02017k","url":null,"abstract":"A Rh(III)-catalyzed dearomative 2,3-diamination of indoles with N-alkoxyamides has been developed. The method provides an efficient approach to access 2-(N-acylimino)-3-aminoindolines with high regioselectivity.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"101 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936514","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this work, we present a UV-induced 6π-cyclization protocol enabling the synthesis of polysubstituted naphthol skeletons using a single cobaloxime catalyst. In addition, the dual-function photosensitizer 4CzIPN served as both an energy transfer (EnT) photosensitizer and a single electron transfer (SET) photocatalyst within the reaction, leading to the synthesis of the same skeleton under visible light irradiation. The sole by-product of the two strategies was hydrogen, offering potential utility.
{"title":"Photoinduced Co-catalyzed dehydrogenative cyclization of 2-alkenylphenyl carbonyl compounds and mechanistic insights","authors":"Hao-Yuan Li, Xiu-Long Yang, Fantao Zhou, Jun-Li Li, Qing-Yuan Meng, Xiaoying Niu","doi":"10.1039/d4qo02132k","DOIUrl":"https://doi.org/10.1039/d4qo02132k","url":null,"abstract":"In this work, we present a UV-induced 6π-cyclization protocol enabling the synthesis of polysubstituted naphthol skeletons using a single cobaloxime catalyst. In addition, the dual-function photosensitizer 4CzIPN served as both an energy transfer (EnT) photosensitizer and a single electron transfer (SET) photocatalyst within the reaction, leading to the synthesis of the same skeleton under visible light irradiation. The sole by-product of the two strategies was hydrogen, offering potential utility.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936537","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rubal Sharma, Mitsuhiro Arisawa, Shinobu Takizawa, Mohamed S. H. Salem
Skeletal editing is an emerging approach in synthetic chemistry that enables precise atom-level modifications within molecular cores, facilitating complex transformations and minimizing resource-intensive synthesis. This review provides a comprehensive overview of the most recent advancements in skeletal editing, with a particular focus on single atom modifications. While skeletal editing can be applied to both cyclic and acyclic compounds, this review centers on carbo- and heterocyclic systems exclusively. By integrating historical context and categorizing key developments, it highlights the major achievements in insertion, deletion, and transmutation, connecting related works and delving into mechanistic insights.
{"title":"Remodelling Molecular Frameworks via Atom-Level Surgery: Recent Advances in Skeletal Editing of (Hetero)Cycles","authors":"Rubal Sharma, Mitsuhiro Arisawa, Shinobu Takizawa, Mohamed S. H. Salem","doi":"10.1039/d4qo02157f","DOIUrl":"https://doi.org/10.1039/d4qo02157f","url":null,"abstract":"Skeletal editing is an emerging approach in synthetic chemistry that enables precise atom-level modifications within molecular cores, facilitating complex transformations and minimizing resource-intensive synthesis. This review provides a comprehensive overview of the most recent advancements in skeletal editing, with a particular focus on single atom modifications. While skeletal editing can be applied to both cyclic and acyclic compounds, this review centers on carbo- and heterocyclic systems exclusively. By integrating historical context and categorizing key developments, it highlights the major achievements in insertion, deletion, and transmutation, connecting related works and delving into mechanistic insights.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The efficient and controllable generation of bridged polycycles of structural complexity and diversity from readily avaialbe feedstocks is highly important for morden organic synthesis, chemical biology and drug discovery. Here we present a unique substitution-hemiketalization cyclization of the readily available bridged benzoxocin-4-ones with Grignard reagents, which leads to a facile synthesis of a diverse portfolio of bridged benzoxocin-2-ol frameworks. The reaction features high regioselectivity and diastereoselectivity, meanwhile accomadating a broad scope of Grignard reagents. The electrophilic capture of organomagnesium intermediates generated in the reaction enables the one-pot access to bridged polycyclic benzoxocin-2-ols with enhanced complexity and diversity. Collectively, this work showcases a conceptional strategy that can efficiently generate structurally rich and complex bridged ring skeletons essentially from phenolic feedstocks.
{"title":"Bridged Rings from Phenolic Feedstocks: Regio- and Diastereoselective Substitution-Hemiketalization Cyclization of Bridged Benzoxocin-4-ones with Grignard Reagents","authors":"Xiaojie Li, Yishuai Fan, Haoran Yang, Ruwei Shen","doi":"10.1039/d4qo02197e","DOIUrl":"https://doi.org/10.1039/d4qo02197e","url":null,"abstract":"The efficient and controllable generation of bridged polycycles of structural complexity and diversity from readily avaialbe feedstocks is highly important for morden organic synthesis, chemical biology and drug discovery. Here we present a unique substitution-hemiketalization cyclization of the readily available bridged benzoxocin-4-ones with Grignard reagents, which leads to a facile synthesis of a diverse portfolio of bridged benzoxocin-2-ol frameworks. The reaction features high regioselectivity and diastereoselectivity, meanwhile accomadating a broad scope of Grignard reagents. The electrophilic capture of organomagnesium intermediates generated in the reaction enables the one-pot access to bridged polycyclic benzoxocin-2-ols with enhanced complexity and diversity. Collectively, this work showcases a conceptional strategy that can efficiently generate structurally rich and complex bridged ring skeletons essentially from phenolic feedstocks.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"82 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936509","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Feng Chen, Yijun Duan, Ye Guo, Yuncheng Liu, Ming Lang, Jin-Bao Peng, Shiyong Peng
An unexpected In(OTf)3-catalyzed cascade reaction of bicyclo[1.1.0]butanes with triazinanes is reported, providing a series of butterfly-shaped biscyclobutenyl amines in good yields. This reaction features simple operation, mild reaction conditions, and broad substrate scope. A rational mechanism involving a key carbocation intermediate is proposed.
{"title":"An Unexpected Lewis Acid-Catalyzed Cascade Reaction of Bicyclo[1.1.0]butanes with Triazinanes to Biscyclobutenyl Amines","authors":"Feng Chen, Yijun Duan, Ye Guo, Yuncheng Liu, Ming Lang, Jin-Bao Peng, Shiyong Peng","doi":"10.1039/d4qo02245a","DOIUrl":"https://doi.org/10.1039/d4qo02245a","url":null,"abstract":"An unexpected In(OTf)3-catalyzed cascade reaction of bicyclo[1.1.0]butanes with triazinanes is reported, providing a series of butterfly-shaped biscyclobutenyl amines in good yields. This reaction features simple operation, mild reaction conditions, and broad substrate scope. A rational mechanism involving a key carbocation intermediate is proposed.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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