| Switchable Radical Carbonylation by Philicity Regulation | |
| Lu, Bin1; Xu, Minghao2; Qi, Xiaotian2; Jiang, Min3; Xiao, Wen-Jing1,5; Chen, Jia-Rong1,4 | |
| 2022-08-17 | |
| Source Publication | Journal of the American Chemical Society Impact Factor & Quartile |
| ISSN | 0002-7863 |
| Volume | 144Issue:32Pages:14923-14935 |
| Abstract | Carbonylation reactions involving CO as readily available C1 synthons have become one of the most important tools for the construction of carbonyl compounds from feedstock chemicals. Despite numerous catalytic methods for carbonylation reactions proceeding via ionic or radical pathways, an inherent limitation to these methods is the need to control switchable single and double carbonylative formation of value-added products from the same and simple starting materials. Here, we describe a new strategy that exploits photoredox catalysis to regulate the philicity of amine coupling partners to drive switchable radical carbonylation reactions. In double carbonylation, amines were first transformed into nitrogen radical cations by single-electron transfer-oxidation and coupled with CO to form carbamoyl radicals, which further underwent radical cross-coupling with the incipient cyanoalkyl acyl radicals to afford the double carbonylation products. Upon the addition of stoichiometric 4-dimethylaminopyridine (DMAP), DMAP competitively traps the initially formed cyanoalkyl acyl radical to form the relatively stabilized cyanoalkyl acyl-DMAP salts that engaged in the subsequent substitution with the nucleophilic amines to produce the single carbonylation products. The reaction proceeded smoothly with excellent selectivity in the presence of various amine nucleophiles at room temperature, generating valuable amides and α-ketoamides in a versatile and controlled fashion. Combined experimental and computational studies provided mechanistic insights into the possible pathways. © 2022 American Chemical Society. |
| Keyword | Amides Carbonyl compounds Carbonylation Free radical reactions 4-dimethylaminopyridine Acyl radicals Carbonylation reactions Carbonylations Catalytic methods Ionic pathways Philicity Radical carbonylation Switchable Synthons |
| Publisher | American Chemical Society |
| DOI | 10.1021/jacs.2c06677 |
| Indexed By | EI |
| Language | 英语 |
| EI Accession Number | 20223412622450 |
| EI Keywords | Amines |
| EI Classification Number | 802.2 Chemical Reactions ; 804.1 Organic Compounds |
| Original Document Type | Journal article (JA) |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | https://ir.lzu.edu.cn/handle/262010/486216 |
| Collection | 兰州大学 化学化工学院 |
| Corresponding Author | Xiao, Wen-Jing; Chen, Jia-Rong |
| Affiliation | 1.Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan; 430079, China; 2.Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan; 430072, China; 3.College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou; 310036, China; 4.School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang; 453007, China; 5.State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou; 730000, China |
| Corresponding Author Affilication | College of Chemistry and Chemical Engineering |
| Recommended Citation GB/T 7714 | Lu, Bin,Xu, Minghao,Qi, Xiaotian,et al. Switchable Radical Carbonylation by Philicity Regulation[J]. Journal of the American Chemical Society,2022,144(32):14923-14935. |
| APA | Lu, Bin,Xu, Minghao,Qi, Xiaotian,Jiang, Min,Xiao, Wen-Jing,&Chen, Jia-Rong.(2022).Switchable Radical Carbonylation by Philicity Regulation.Journal of the American Chemical Society,144(32),14923-14935. |
| MLA | Lu, Bin,et al."Switchable Radical Carbonylation by Philicity Regulation".Journal of the American Chemical Society 144.32(2022):14923-14935. |
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