| Switchable Radical Carbonylation by Philicity Regulation | |
| Lu, Bin1; Xu, Minghao2; Qi, Xiaotian2; Jiang, Min3; Xiao, Wen-Jing1,4; Chen, Jia-Rong1,5 | |
| 2022-08-17 | |
| Source Publication | Journal of the American Chemical Society Impact Factor & Quartile |
| ISSN | 0002-7863 |
| EISSN | 1520-5126 |
| Volume | 144Issue:32Pages:14923-14935 |
| page numbers | 13 |
| 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 same and simple starting materials. Here, we describe a new strategy that exploits photoredox catalysis to regulate the philicity 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 alpha-ketoamides in a versatile and controlled fashion. Combined experimental and computational studies provided mechanistic insights into the possible pathways. |
| Publisher | AMER CHEMICAL SOC |
| DOI | 10.1021/jacs.2c06677 |
| Indexed By | SCIE ; IC |
| Language | 英语 |
| WOS Research Area | Chemistry |
| WOS Subject | Chemistry, Multidisciplinary |
| WOS ID | WOS:000843490400001 |
| Original Document Type | Article |
| PMID | 3593979 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | https://ir.lzu.edu.cn/handle/262010/488816 |
| Collection | 兰州大学 |
| Corresponding Author | Xiao, Wen-Jing; Chen, Jia-Rong |
| Affiliation | 1.Cent China Normal Univ, Coll Chem, Key Lab Pesticides & Chem Biol, Minist Educ, Wuhan 430079, Peoples R China; 2.Wuhan Univ, Coll Chem & Mol Sci, Mat, Minist Educ, R China, Wuhan 430072, Peoples R China; 3.Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Hangzhou 310036, Peoples R China; 4.Lanzhou Univ, State Key Lab Appl Organ Chem, Lanzhou 730000, Peoples R China; 5.Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China |
| 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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