Bei Chen, Zhimeng Song, Yukun Chen, Xingru Yan, Ge Zhang, Qian Zhang
{"title":"Photoredox/Cobalt Dual-Catalyzed Regioselective Hydroalkoxylation of 1,3-Dienes with Alcohols","authors":"Bei Chen, Zhimeng Song, Yukun Chen, Xingru Yan, Ge Zhang, Qian Zhang","doi":"10.1039/d5qo00777a","DOIUrl":null,"url":null,"abstract":"Catalytic hydroalkoxylation of alkenes with oxygen-nucleophiles is of great interest and importance but remains an under developing task in synthetic chemistry. Here, we developed a photoredox and Co-catalyzed regioselective hydroalkoxylation of 1,3-dienes with alcohols, which enables efficient access to valuable allylic ethers in good to excellent yields. The reaction features mild conditions, good functional group tolerance, and wide substrate scope. Application of this rection to late-stage functionalization of relatively complex natural products and bioactive molecules further increases the utility of the developed methodology. Mechanistic studies suggest that the reaction underwent a CoH-mediated hydrogen atom transfer (HAT) to 1,3-diene, followed by a radical-polar crossover process involving nucleophilic displacement of allylic cobalt(IV) with free alcohols. This reaction is an important complement to the arsenal of transition-metal-catalyzed hydroalkoxylation of alkenes, providing a new strategy to deliver valuable allylic ethers.","PeriodicalId":97,"journal":{"name":"Organic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":4.7000,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Chemistry Frontiers","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5qo00777a","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
Catalytic hydroalkoxylation of alkenes with oxygen-nucleophiles is of great interest and importance but remains an under developing task in synthetic chemistry. Here, we developed a photoredox and Co-catalyzed regioselective hydroalkoxylation of 1,3-dienes with alcohols, which enables efficient access to valuable allylic ethers in good to excellent yields. The reaction features mild conditions, good functional group tolerance, and wide substrate scope. Application of this rection to late-stage functionalization of relatively complex natural products and bioactive molecules further increases the utility of the developed methodology. Mechanistic studies suggest that the reaction underwent a CoH-mediated hydrogen atom transfer (HAT) to 1,3-diene, followed by a radical-polar crossover process involving nucleophilic displacement of allylic cobalt(IV) with free alcohols. This reaction is an important complement to the arsenal of transition-metal-catalyzed hydroalkoxylation of alkenes, providing a new strategy to deliver valuable allylic ethers.
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.