{"title":"Aldehyde–Olefin Couplings Via Sulfoxylate-Mediated Oxidative Generation of Ketyl Radical Anions","authors":"Zhihang Li, Joseph A. Tate, Adam Noble","doi":"10.1021/jacs.4c10093","DOIUrl":null,"url":null,"abstract":"Ketyl radicals are valuable reactive intermediates because they allow carbonyl chemistry to be extended beyond traditional electrophilic reactivity through simple single-electron reduction to a nucleophilic radical. However, this pathway is challenging due to the large negative reduction potentials of carbonyls, thus requiring highly reducing conditions. Herein, we describe the development of an alternative strategy to access ketyl radicals from aldehydes, which avoids the reduction pathway by instead proceeding via single-electron oxidation and desulfination of α-hydroxy sulfinates. These redox-active aldehyde adducts are generated <i>in situ</i> through the addition of sulfoxylate (SO<sub>2</sub><sup>2–</sup>) to aldehydes and possess low oxidation potentials, thereby facilitating ketyl radical formation and circumventing the need for strongly reducing conditions. We demonstrate the application of this sulfoxylate-mediated ketyl radical formation in ketyl–olefin coupling reactions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c10093","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Ketyl radicals are valuable reactive intermediates because they allow carbonyl chemistry to be extended beyond traditional electrophilic reactivity through simple single-electron reduction to a nucleophilic radical. However, this pathway is challenging due to the large negative reduction potentials of carbonyls, thus requiring highly reducing conditions. Herein, we describe the development of an alternative strategy to access ketyl radicals from aldehydes, which avoids the reduction pathway by instead proceeding via single-electron oxidation and desulfination of α-hydroxy sulfinates. These redox-active aldehyde adducts are generated in situ through the addition of sulfoxylate (SO22–) to aldehydes and possess low oxidation potentials, thereby facilitating ketyl radical formation and circumventing the need for strongly reducing conditions. We demonstrate the application of this sulfoxylate-mediated ketyl radical formation in ketyl–olefin coupling reactions.
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.