Selective Transfer Hydrogenation of C=O and Conjugated C=C Bonds Using An NHC‐Based Pincer (CNC)MnI Complex in Methanol

Base metal catalyzed transfer hydrogenation reactions using methanol is highly challenging. Employing a single N‐heterocyclic carbene (NHC)‐based pincer (CNC)MnI complex, chemoselective single and double transfer hydrogenation of α, β‐unsaturated ketones to saturated ketones or alcohols by utilizing methanol as the hydrogen source is disclosed. The protocol was tolerant towards the selective transfer hydrogenation of C=C or C=O bonds in the presence of several other reducible functional groups and led to the synthesis of several biologically relevant molecules and natural products. Notably, this is the first report of a Mn‐catalyzed transfer hydrogenation of carbonyl groups with methanol. Several control experiments, kinetic studies, Hammett studies, and density functional theory (DFT) calculations were carried out to understand the mechanistic details of this catalytic process.