{"title":"Triflic acid catalyzed intermolecular hydroamination of alkenes with Fmoc-NH<sub>2</sub> as the amine source.","authors":"Aswathi C S, Chinraj Sivarajan, Raja Mitra","doi":"10.1039/d5ob00519a","DOIUrl":null,"url":null,"abstract":"<p><p>Intermolecular hydroamination of alkenes is recognized as one of the most challenging synthetic pathways for directly obtaining primary amine derivatives from alkenes. While metal-catalyzed hydroamination is well established, metal-free hydroamination for synthesizing primary amines remains an attractive yet infrequent approach. In this study, we report the hydroamination of vinyl arenes using triflic acid as the catalyst and Fmoc-NH<sub>2</sub> as the amine source. The optimized conditions proved effective for a range of vinyl arenes and some endocyclic alkenes, yielding moderate to excellent results (40-91%). Mechanistic investigations conducted through NMR, variable temperature NMR, kinetic studies, and control reactions indicated that the transient interaction between triflic acid and Fmoc-NH<sub>2</sub> inhibited styrene polymerization. Primary amines were obtained by deprotecting the Fmoc group using KOH/MeOH.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":" ","pages":""},"PeriodicalIF":2.9000,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5ob00519a","RegionNum":3,"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
Intermolecular hydroamination of alkenes is recognized as one of the most challenging synthetic pathways for directly obtaining primary amine derivatives from alkenes. While metal-catalyzed hydroamination is well established, metal-free hydroamination for synthesizing primary amines remains an attractive yet infrequent approach. In this study, we report the hydroamination of vinyl arenes using triflic acid as the catalyst and Fmoc-NH2 as the amine source. The optimized conditions proved effective for a range of vinyl arenes and some endocyclic alkenes, yielding moderate to excellent results (40-91%). Mechanistic investigations conducted through NMR, variable temperature NMR, kinetic studies, and control reactions indicated that the transient interaction between triflic acid and Fmoc-NH2 inhibited styrene polymerization. Primary amines were obtained by deprotecting the Fmoc group using KOH/MeOH.
期刊介绍：
Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.
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