Manganese‐Catalyzed β‐Methylation of Alcohols by Methanol

We report an earth‐abundant‐metal‐catalyzed double and single methylation of alcohols. A manganese catalyst, which operates at low catalyst loadings and short reaction times, mediates these reactions efficiently. A broad scope of primary and secondary alcohols, including purely aliphatic examples, and 1,2‐aminoalcohols can be methylated. Furthermore, alcohol methylation for the synthesis of pharmaceuticals has been demonstrated. The catalyst system tolerates many functional groups among them hydrogenation‐sensitive examples and upscaling is easily achieved. Mechanistic investigations are indicative of a borrowing hydrogen or hydrogen autotransfer mechanism involving a bimetallic K‐Mn catalyst. The catalyst accepts hydrogen as a proton and a hydride from alcohols efficiently and reacts with a chalcone via hydride transfer. Einzel oder Doppel? Ein Mn‐basierter Katalysator ermöglicht die effiziente Einzelmethylierung sekundärer Kohlenstoffatome und Doppelmethylierung primärer Kohlenstoffatome von primären und sekundären Alkoholen, einschließlich rein aliphatischen Beispielen. Der Katalysator toleriert viele funktionelle Gruppen, agiert bei niedrigen Katalysatorbeladungen sowie kurzen Reaktionszeiten und ermöglicht einfache Maßstabsvergrößerung.