Jia-Wei Song, Fang Xia, Xiu-Lan Zhang and Cheng-Pan Zhang
{"title":"Pd-catalyzed relay Heck arylation of alkenyl alcohols with arylsulfonium salts†","authors":"Jia-Wei Song, Fang Xia, Xiu-Lan Zhang and Cheng-Pan Zhang","doi":"10.1039/D4QO00618F","DOIUrl":null,"url":null,"abstract":"<p >A palladium-catalyzed tandem Heck arylation and isomerization of alkenyl alcohols using arylsulfonium salts is reported. The reaction enabled facile conversion of various allylic and non-allylic alcohols to the corresponding arylalkyl ketones or aldehydes in good to excellent yields. Different types of arylsulfonium salts were verified as powerful arylation reagents in the relay Heck reactions <em>via</em> chain-walking without being affected by the sulfide byproducts. The transformation exhibited obvious advantages such as high efficiency, mild conditions, good functional group tolerance, excellent regioselectivity, and a wide range of substrates, which allowed remote functionalization of alkenyl alcohols with more complex aryl transfer reagents. A plausible reaction mechanism was presumed to involve the initial Heck arylation of the alkenyl moiety with arylsulfonium salts, repeated migratory insertion and β-hydride elimination, and enol isomerization to yield the final product. Moreover, the Pd-catalyst remains coordinated to the substrate during the relay process. This work represents the first remote functionalization of alkenyl alcohols with arylsulfonium salts as the arylation reagents.</p>","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/qo/d4qo00618f","RegionNum":1,"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
A palladium-catalyzed tandem Heck arylation and isomerization of alkenyl alcohols using arylsulfonium salts is reported. The reaction enabled facile conversion of various allylic and non-allylic alcohols to the corresponding arylalkyl ketones or aldehydes in good to excellent yields. Different types of arylsulfonium salts were verified as powerful arylation reagents in the relay Heck reactions via chain-walking without being affected by the sulfide byproducts. The transformation exhibited obvious advantages such as high efficiency, mild conditions, good functional group tolerance, excellent regioselectivity, and a wide range of substrates, which allowed remote functionalization of alkenyl alcohols with more complex aryl transfer reagents. A plausible reaction mechanism was presumed to involve the initial Heck arylation of the alkenyl moiety with arylsulfonium salts, repeated migratory insertion and β-hydride elimination, and enol isomerization to yield the final product. Moreover, the Pd-catalyst remains coordinated to the substrate during the relay process. This work represents the first remote functionalization of alkenyl alcohols with arylsulfonium salts as the arylation reagents.
期刊介绍:
Organic Chemistry Frontiers is an esteemed journal that publishes high-quality research across the field of organic chemistry. It places a significant emphasis on studies that contribute substantially to the field by introducing new or significantly improved protocols and methodologies. The journal covers a wide array of topics which include, but are not limited to, organic synthesis, the development of synthetic methodologies, catalysis, natural products, functional organic materials, supramolecular and macromolecular chemistry, as well as physical and computational organic chemistry.