{"title":"Copper-Catalyzed Borrowing Hydrogen Reaction for α-Alkylation of Amides with Alcohols","authors":"Qiuling Xia, Yulong Miao, Yue Hu, Yinjun Xie* and Junfei Luo*, ","doi":"10.1021/acs.joc.4c00404","DOIUrl":null,"url":null,"abstract":"<p >We report the first example of copper-catalyzed α-alkylation of acetamides with alcohols via a borrowing hydrogen strategy. Catalyzed by the <i>in situ</i>-generated copper particles, acetamides and various substituted benzyl or alkyl alcohols were transformed into functionalized amides in good yields with excellent selectivity. Compared with previous work, this process is simple using commercially available Cu(OAc)<sub>2</sub> as a precatalyst, without an additional ligand or a metal complex, and easier. Mechanistic studies revealed that aldehyde and α,β-unsaturated amides were the intermediates of this reaction and also disclosed the role of copper in alcohol dehydrogenation and C═C bond hydrogenation.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3000,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Organic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.joc.4c00404","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
We report the first example of copper-catalyzed α-alkylation of acetamides with alcohols via a borrowing hydrogen strategy. Catalyzed by the in situ-generated copper particles, acetamides and various substituted benzyl or alkyl alcohols were transformed into functionalized amides in good yields with excellent selectivity. Compared with previous work, this process is simple using commercially available Cu(OAc)2 as a precatalyst, without an additional ligand or a metal complex, and easier. Mechanistic studies revealed that aldehyde and α,β-unsaturated amides were the intermediates of this reaction and also disclosed the role of copper in alcohol dehydrogenation and C═C bond hydrogenation.
期刊介绍:
The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.