Qikun Wu, Prof. Dr. Kei Muto, Prof. Dr. Junichiro Yamaguchi
{"title":"钯催化氮的c2选择性C−H胺化研究","authors":"Qikun Wu, Prof. Dr. Kei Muto, Prof. Dr. Junichiro Yamaguchi","doi":"10.1002/ceur.202400092","DOIUrl":null,"url":null,"abstract":"<p>The site-selective C−H amination of azines is a critical challenge due to the broad applications of amino azines in biologically important compounds. In this work, we report a conceptually novel approach to the electrophilic C2-selective C−H amination of azines using <i>O</i>-benzoylhydroxylamines, catalyzed by a benzyl–palladium complex. A key feature of this transformation is the formation of the distal C−N bond via a benzyl–Pd intermediate, facilitated by a malonate substituent on the azine as a remote directing group. This strategy effectively overrides the inherent polarity mismatch typically observed in electrophilic C2-C−H aminations. The reaction exhibits high site-selectivity and demonstrates towards amine-sensitive functional group, highlighting its synthetic utility.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 2","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400092","citationCount":"0","resultStr":"{\"title\":\"An Umpolung Approach for C2-Selective C−H Amination of Azines by Palladium Catalysis\",\"authors\":\"Qikun Wu, Prof. Dr. Kei Muto, Prof. Dr. Junichiro Yamaguchi\",\"doi\":\"10.1002/ceur.202400092\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The site-selective C−H amination of azines is a critical challenge due to the broad applications of amino azines in biologically important compounds. In this work, we report a conceptually novel approach to the electrophilic C2-selective C−H amination of azines using <i>O</i>-benzoylhydroxylamines, catalyzed by a benzyl–palladium complex. A key feature of this transformation is the formation of the distal C−N bond via a benzyl–Pd intermediate, facilitated by a malonate substituent on the azine as a remote directing group. This strategy effectively overrides the inherent polarity mismatch typically observed in electrophilic C2-C−H aminations. The reaction exhibits high site-selectivity and demonstrates towards amine-sensitive functional group, highlighting its synthetic utility.</p>\",\"PeriodicalId\":100234,\"journal\":{\"name\":\"ChemistryEurope\",\"volume\":\"3 2\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2025-02-03\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400092\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemistryEurope\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/ceur.202400092\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemistryEurope","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/ceur.202400092","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
An Umpolung Approach for C2-Selective C−H Amination of Azines by Palladium Catalysis
The site-selective C−H amination of azines is a critical challenge due to the broad applications of amino azines in biologically important compounds. In this work, we report a conceptually novel approach to the electrophilic C2-selective C−H amination of azines using O-benzoylhydroxylamines, catalyzed by a benzyl–palladium complex. A key feature of this transformation is the formation of the distal C−N bond via a benzyl–Pd intermediate, facilitated by a malonate substituent on the azine as a remote directing group. This strategy effectively overrides the inherent polarity mismatch typically observed in electrophilic C2-C−H aminations. The reaction exhibits high site-selectivity and demonstrates towards amine-sensitive functional group, highlighting its synthetic utility.