Zhang, GuoyingIrrgang, TorstenDietel, ThomasKallmeier, FabianKempe, Rhett2026-07-032026-07-031433-7851PubMed:29718552ORCID:/0000-0001-7073-2766/work/219173127https://hdl.handle.net/1885/733812778Catalysis with earth-abundant transition metals is an option to help save our rare noble-metal resources and is especially interesting when novel reactivity or selectivity patterns are observed. We report here on a novel reaction, namely the dehydrogenative alkylation or α-olefination of alkyl-substituted N-heteroarenes with alcohols. Manganese complexes developed in our laboratory catalyze the reaction with high efficiency whereas iron and cobalt complexes stabilized by the same ligands are essentially inactive. Hydrogen is liberated during the reaction, and bromine and iodine functional groups as well as olefins are tolerated. A variety of alkyl-substituted N-heteroarenes can be functionalized, and benzylic and aliphatic alcohols undergo the reaction.We thank Anna-Maria Dietel for her excellent help in the laboratory and the Deutsche Forschungsgemeinschaft (KE-756/29-1, 31-1), the Shandong Provincial Natural Science Foundation of China (ZR2017MB029, ZR2017BB060), and the Alexander von Humboldt Foundation for financial support.5enPublisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimalcoholsdehydrogenationmanganeseN-heteroarenesolefination2018-07-1610.1002/anie.20180157385047750930