{"title":"光诱导铜催化烃类的kharasch型卤化烷基化。","authors":"Yuan Cai, Mahiob Dawor, Gaurav Gaurav, Tobias Ritter","doi":"10.1021/jacs.5c05699","DOIUrl":null,"url":null,"abstract":"<p><p>The simultaneous construction of C-C and C-X bonds in a single step facilitates multistep synthesis through rapid carbon chain growth and subsequent transformations of halide functionalities. Traditional Kharasch addition requires simple polyhalogenated compounds or those with electron-withdrawing groups at the α-carbon. Herein, we present a Kharasch-type reaction utilizing a broad range of carboxylic acid-derived redox-active esters as the alkyl source, which enables the efficient introduction of highly functionalized alkyl groups. Our method produces α-halo carbonyls that enable versatile nucleophilic substitutions for synthesizing valuable compounds, such as unnatural α-amino acids.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"18438-18444"},"PeriodicalIF":15.6000,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12147127/pdf/","citationCount":"0","resultStr":"{\"title\":\"Kharasch-Type Haloalkylation of Alkenes by Photoinduced Copper Catalysis.\",\"authors\":\"Yuan Cai, Mahiob Dawor, Gaurav Gaurav, Tobias Ritter\",\"doi\":\"10.1021/jacs.5c05699\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The simultaneous construction of C-C and C-X bonds in a single step facilitates multistep synthesis through rapid carbon chain growth and subsequent transformations of halide functionalities. Traditional Kharasch addition requires simple polyhalogenated compounds or those with electron-withdrawing groups at the α-carbon. Herein, we present a Kharasch-type reaction utilizing a broad range of carboxylic acid-derived redox-active esters as the alkyl source, which enables the efficient introduction of highly functionalized alkyl groups. Our method produces α-halo carbonyls that enable versatile nucleophilic substitutions for synthesizing valuable compounds, such as unnatural α-amino acids.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\" \",\"pages\":\"18438-18444\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-06-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12147127/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jacs.5c05699\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/5/20 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.5c05699","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/5/20 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Kharasch-Type Haloalkylation of Alkenes by Photoinduced Copper Catalysis.
The simultaneous construction of C-C and C-X bonds in a single step facilitates multistep synthesis through rapid carbon chain growth and subsequent transformations of halide functionalities. Traditional Kharasch addition requires simple polyhalogenated compounds or those with electron-withdrawing groups at the α-carbon. Herein, we present a Kharasch-type reaction utilizing a broad range of carboxylic acid-derived redox-active esters as the alkyl source, which enables the efficient introduction of highly functionalized alkyl groups. Our method produces α-halo carbonyls that enable versatile nucleophilic substitutions for synthesizing valuable compounds, such as unnatural α-amino acids.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.