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Direct and site\u2010selective C\u2212H bond amination of arenes provides the most efficient and convenient method to prepare aminoarenes. A main challenge is to selectively install the amino group (or other functional groups) to the distal <jats:italic>para\u2010<\/jats:italic>carbon of arenes (especially multi\u2010substituted arenes) during the C\u2212H bond functionalization events. Herein, we address this problem by designing a new strategy via a sequential radical dearomatization\/radical amination\/rearomatization process for <jats:italic>para<\/jats:italic>\u2010selective amination of benzyl alcohols. The <jats:italic>para<\/jats:italic>\u2010selectivity of our reaction is completely independent of the electronic and steric properties of the other substituents of the arene substrates. Aminoarenes with many substituents (up to full substitution) and diverse substitution patterns, including those difficult to synthesize previously, could be readily prepared using our protocols. Further exploration of the current strategy shall lead to other challenging C\u2212H functionalization of arenes.<\/jats:p>","DOI":"10.1002\/anie.202407293","type":"journal-article","created":{"date-parts":[[2024,7,27]],"date-time":"2024-07-27T18:48:58Z","timestamp":1722106138000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Photocatalytic Direct <i>Para<\/i>\u2010Selective C\u2212H Amination of Benzyl Alcohols: Selectivity Independent of Side Substituents"],"prefix":"10.1002","author":[{"given":"Donghan","family":"Liu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education Center for R&amp;D of Fine Chemicals of Guizhou University  Guiyang 550025 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ting","family":"Tu","sequence":"additional","affiliation":[{"name":"State Key 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