Metalloradical Catalysed Olefin Hydrogenation: A New Approach To Radical Hydrogenation

Metalloradical Catalysed Olefin Hydrogenation: A New Approach To Radical Hydrogenation

Radical hydrogenation via Hydrogen Atom Transfer (HAT)/ Transfer Hydrogenation to alkenes is an increasingly important transformation for the formation of thermodynamically more stable alkane isomers. Current single-catalyst-based hydrogenation methods require a stoichiometric oxidant in addition to a hydride (H⁻) source. Hydrogenation based on radical, metal-catalysed hydrogen atom transfer (mHAT), transfer hydrogenation mechanisms offers an outstanding opportunity to overcome these difficulties, enabling the mild reduction of these challenging olefins with selectivity that is complementary to traditional hydrogenations with H₂.

Furthermore, it provides an opportunity for asymmetric induction through transfer hydrogenation using two different hydrogen sources. Herein, we disclose the first report on metalloradical (MRC) catalysed radical hydrogenation of olefins using two distinct hydrogen sources . Control reaction confirms the generation of the H₂ molecule, which is further activated and subsequently donated to olefins via MRC-catalysed HAT. The bimetallic nature of MRC makes it even oxidant free. The mechanistic insights suggest the radical hydrogenation pathway. Together, this catalytic system allows us to hydrogenate different classes of molecules and introduces a new approach to radical hydrogenation. currently the asymmetric version of the process is being developed by changing the alkyl group and substituent on ligand moiety.