{"title":"DFT study on mechanism of nickel-catalyzed decarbonylative reductive alkylation of aroyl fluorides with alkyl bromides","authors":"Lijuan Liu, Zhenfeng Shang, Ruifang Li, Xiufang Xu","doi":"10.1016/j.tetlet.2024.155353","DOIUrl":null,"url":null,"abstract":"<div><div>The mechanism of the nickel-catalyzed decarbonylative reductive alkylation of aroyl fluorides with alkyl bromides is investigated using density functional theory calculations. The calculation result shows that the reaction mechanism involves sequential steps of C–F bond oxidative addition, decarbonylation, alkyl radical addition, C(sp<sup>2</sup>)–C(sp<sup>3</sup>) reductive elimination to afford the product, single electron transfer (SET) and reduction by Zn to regenerate the initiating complex. And the step of C–F bond oxidative addition was found to be the rate-determining step. The decarbonylation should occur before the alkyl radical addition. The effects of 1,3-bis(diphenylphosphino)propane (DPPP) ligand and different substrates on the reactivity were also analyzed. These calculation results disclosed the detailed reaction mechanism and shed lights on some ambiguous suggestions from experiments.</div></div>","PeriodicalId":438,"journal":{"name":"Tetrahedron Letters","volume":"152 ","pages":"Article 155353"},"PeriodicalIF":1.5000,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Tetrahedron Letters","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0040403924004489","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
The mechanism of the nickel-catalyzed decarbonylative reductive alkylation of aroyl fluorides with alkyl bromides is investigated using density functional theory calculations. The calculation result shows that the reaction mechanism involves sequential steps of C–F bond oxidative addition, decarbonylation, alkyl radical addition, C(sp2)–C(sp3) reductive elimination to afford the product, single electron transfer (SET) and reduction by Zn to regenerate the initiating complex. And the step of C–F bond oxidative addition was found to be the rate-determining step. The decarbonylation should occur before the alkyl radical addition. The effects of 1,3-bis(diphenylphosphino)propane (DPPP) ligand and different substrates on the reactivity were also analyzed. These calculation results disclosed the detailed reaction mechanism and shed lights on some ambiguous suggestions from experiments.
期刊介绍：
Tetrahedron Letters provides maximum dissemination of outstanding developments in organic chemistry. The journal is published weekly and covers developments in techniques, structures, methods and conclusions in experimental and theoretical organic chemistry. Rapid publication of timely and significant research results enables researchers from all over the world to transmit quickly their new contributions to large, international audiences.
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