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Manganese‐Catalyzed β‐Methylation of Alcohols by Methanol
Author(s) -
Schlagbauer Martin,
Kallmeier Fabian,
Irrgang Torsten,
Kempe Rhett
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201912055
Subject(s) - catalysis , chemistry , bimetallic strip , hydride , manganese , alcohol , methanol , hydrogen , methylation , organic chemistry , combinatorial chemistry , biochemistry , gene
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.