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, ß-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.

Cyclometalated (NNC)Ru(II) complex catalyzed ß-methylation of alcohols using methanol.

Indolyl fragment containing phenanthroline based new ligands and their corresponding Ru(II) complexes were synthesized and fully characterized by various spectroscopic techniques. The catalytic activity of these newly synthesized cyclometalated (NNC)Ru(II) complexes was explored towards the ß-methylation of alcohols using methanol. Notably, these complexes displayed superior reactivity compared to various (NNN)Ru(II) complexes. Utilizing this strategy, a wide range of primary, secondary, and aliphatic straight chain alcohols were selectively methylated. This protocol was further employed for the methylation of a few natural products and the gram scale synthesis of ß-methylated alcohols. A series of control experiments and kinetic studies were performed to understand the plausible reaction mechanism.

Cooperative Mn(i)-complex catalyzed transfer hydrogenation of ketones and imines.

The synthesis and reactivity of Mn(i) complexes bearing bifunctional ligands comprising both the amine N-H and benzimidazole fragments are reported. Among the various ligands, the N-((1H-benzimidazol-2-yl)methyl)aniline ligand containing Mn(i) complex presented higher reactivity in the transfer hydrogenation (TH) of ketones in 2-propanol. Experimentally, it was established that both the benzimidazole and amine N-H proton played a vital role in the enhancement of the catalytic activity. Utilizing this system a wide range of aldehydes and ketones were reduced efficiently. Notably, the TH of several imines, as well as chemoselective reduction of unsaturated ketones, was achieved in the presence of this catalyst. DFT calculations were carried out to understand the plausible reaction mechanism which disclosed that the transfer hydrogenation reaction followed a concerted outer-sphere mechanism.

Cobalt complex catalyzed atom-economical synthesis of quinoxaline, quinoline and 2-alkylaminoquinoline derivatives.

A new phosphine-free Co(ii) complex-catalyzed synthesis of various quinoxalines via dehydrogenative coupling of vicinal diols with both o-phenylenediamines and 2-nitroanilines is reported. This complex was also effective for the synthesis of quinolines. The practical aspect of this catalytic system was revealed by the one-pot synthesis of 2-alkylaminoquinolines.