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However, conventional synthetic methods for these amines typically involve tedious multi\u2010step processes with suboptimal efficiency and cost\u2010effectiveness. Direct amination of readily available alcohols to access primary amines is highly appealing but remains challenging. Herein, we report a manganese\u2010catalyzed transamination of alcohols using commercially available benzylamine as the amination reagent. The protocol demonstrates broad substrate compatibility and excellent selectivity toward aliphatic primary amines even at low catalyst loadings, up to 1.1\u00d710\n                    <jats:sup>6<\/jats:sup>\n                    TON could be achieved. Mechanistic studies reveal that bases play crucial roles in achieving excellent selectivity, in which\n                    <jats:italic>t<\/jats:italic>\n                    BuOK facilitates imine intermediate rearrangement and KOH acts as a nucleophile to promote imine bond cleavage, thus enabling the formation of desired primary amines instead of conventional\n                    <jats:italic>N<\/jats:italic>\n                    \u2010alkylated secondary amines.\n                  <\/jats:p>","DOI":"10.1002\/anie.2797925","type":"journal-article","created":{"date-parts":[[2026,3,24]],"date-time":"2026-03-24T05:16:17Z","timestamp":1774329377000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Manganese\u2010Catalyzed Direct Transamination of Aliphatic Alcohols to Primary Amines"],"prefix":"10.1002","volume":"65","author":[{"given":"Jiale","family":"Ji","sequence":"first","affiliation":[{"name":"State Key Laboratory of High\u2010efficiency Utilization of Coal and Green Chemical Engineering School of Chemistry and Chemical Engineering Ningxia University  Yinchuan China"},{"name":"State Key Laboratory of Green Chemical Synthesis and Conversion Department of Chemistry Fudan University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shiliang","family":"Wang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of High\u2010efficiency Utilization of Coal and Green Chemical Engineering School of Chemistry and Chemical Engineering Ningxia University  Yinchuan China"},{"name":"Anhui Province Key Laboratory of Value\u2010Added Catalytic Conversion and Reaction Engineering School of Chemistry and Chemical Engineering Hefei University of Technology  Hefei China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qingshu","family":"Zheng","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Green Chemical Synthesis and 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