{"title":"光氧化与镍催化的结合:乙烯基卤化物和 α-硅胺向叔烯丙基烷基胺的无配位交叉偶联反应","authors":"Fu Ye, Shiming Tong and Weiming Yuan*, ","doi":"10.1021/acscatal.4c02602","DOIUrl":null,"url":null,"abstract":"<p >A ligand-free cross-coupling of vinyl halides and α-silylamines toward tertiary allylic alkylamines by merging nickel and photoredox catalysis is developed. A variety of (<i>E</i>)-vinyl electrophiles including conjugate divinyl halides and sterically hindered vinyl halides are coupled smoothly with α-silylamines to afford allylic amines under mild conditions with good yields and <i>E</i>-selectivity. Moreover, by simply modifying the photocatalyst or prolonging the irradiation time, the reaction can afford <i>Z</i>-selective allylic amines as major products via photochemically driven <i>E</i> → <i>Z</i> isomerization. This radical-based coupling strategy provides an alternative and efficient pathway to construct tertiary allylic alkylamines with good and tunable <i>Z</i>/<i>E</i> selectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3000,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Merging Photoredox and Nickel Catalysis: A Ligand-Free Cross-Coupling of Vinyl Halides and α-Silylamines toward Tertiary Allylic Alkylamines\",\"authors\":\"Fu Ye, Shiming Tong and Weiming Yuan*, \",\"doi\":\"10.1021/acscatal.4c02602\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >A ligand-free cross-coupling of vinyl halides and α-silylamines toward tertiary allylic alkylamines by merging nickel and photoredox catalysis is developed. A variety of (<i>E</i>)-vinyl electrophiles including conjugate divinyl halides and sterically hindered vinyl halides are coupled smoothly with α-silylamines to afford allylic amines under mild conditions with good yields and <i>E</i>-selectivity. Moreover, by simply modifying the photocatalyst or prolonging the irradiation time, the reaction can afford <i>Z</i>-selective allylic amines as major products via photochemically driven <i>E</i> → <i>Z</i> isomerization. This radical-based coupling strategy provides an alternative and efficient pathway to construct tertiary allylic alkylamines with good and tunable <i>Z</i>/<i>E</i> selectivity.</p>\",\"PeriodicalId\":9,\"journal\":{\"name\":\"ACS Catalysis \",\"volume\":null,\"pages\":null},\"PeriodicalIF\":11.3000,\"publicationDate\":\"2024-06-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Catalysis \",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acscatal.4c02602\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acscatal.4c02602","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
通过合并镍催化和光氧化催化,开发了乙烯基卤化物和 α-硅烷基胺向叔烯丙基烷基胺的无配体交叉偶联。包括共轭二乙烯基卤化物和立体受阻乙烯基卤化物在内的多种 (E) - 乙烯基亲电体在温和的条件下与α-硅烷基胺顺利偶联,生成烯丙基胺,并具有良好的产率和 E 选择性。此外,只需改变光催化剂或延长辐照时间,该反应就能通过光化学驱动的 E → Z 异构化得到 Z 选择性烯丙基胺作为主要产物。这种基于自由基的偶联策略为构建具有良好和可调 Z/E 选择性的叔烯丙基烷基胺提供了另一种高效途径。
Merging Photoredox and Nickel Catalysis: A Ligand-Free Cross-Coupling of Vinyl Halides and α-Silylamines toward Tertiary Allylic Alkylamines
A ligand-free cross-coupling of vinyl halides and α-silylamines toward tertiary allylic alkylamines by merging nickel and photoredox catalysis is developed. A variety of (E)-vinyl electrophiles including conjugate divinyl halides and sterically hindered vinyl halides are coupled smoothly with α-silylamines to afford allylic amines under mild conditions with good yields and E-selectivity. Moreover, by simply modifying the photocatalyst or prolonging the irradiation time, the reaction can afford Z-selective allylic amines as major products via photochemically driven E → Z isomerization. This radical-based coupling strategy provides an alternative and efficient pathway to construct tertiary allylic alkylamines with good and tunable Z/E selectivity.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.