Phosphine‐Free NNN‐Manganese(II) Catalyzed C‐alkylation of Methyl N‐Heteroarenes via Borrowing Hydrogen

Abstract Mn(II)‐catalyzed alkylations of methyl N ‐heteroarenes was reported via borrowing hydrogen strategy with alcohols as the alkylating reagent. The developed geometry‐constrained benzimidazole‐iminopyridyl ligand played a key role in promoting the transformation and stablizing the metal center. A wide range of alcohols (aromatic, heteroaromatic and aliphatic) and methyl N ‐Heteroarenes could be able to apply in the current catalytic system, with TON up to 7400.