Manganese(I)-Catalyzed Transfer Hydrogenation and Acceptorless Dehydrogenative Condensation: Promotional Influence of the Uncoordinated N-Heterocycle

The four bidentate manganese(I) complexes [(C5H4N-C5H3N-OH)Mn(CO)(3)Br] (1), [(C9H6N-C5H3N-OH)Mn(CO)(3)Br] (2), [(C8H5N2-C5H3N-OH)Mn(CO)(3)Br] (3), and [(C8H5N2-C5H3N-OCH3)Mn(CO)(3)Br] (4) were synthesized. These complexes were tested as catalysts for the transfer hydrogenation of ketones, and 3 showed the highest activity. The reactions proceeded well with 0.5 mol % of catalyst loading and 20 mol % of t-BuOK at 85 degrees C for 24 h. Furthermore, 3 was also used as a catalyst for the synthesis of primary alcohols via transfer hydrogenation of aldehydes and the synthesis of 1,2-disubstituted benzimidazoles and quinolines via acceptorless dehydrogenative condensations.