Herewith, we report the enantioselective epoxidation of electron‐deficient cis‐ and trans‐α,β‐unsaturated amides with the environmentally benign oxidant H2O2. The catalysts ‐ manganese complexes with bis‐amino‐bis‐pyridine and structurally related ligands ‐ exhibit reasonably high efficiency (up to 100 TON) and excellent chemo‐ and enantioselectivity (up to 100% and 99% ee, respectively). Crucially, the cis‐enamides epoxidation enantioselectivity and yield are dramatically enhanced by the presence of NH‐moiety, which effect can be explained by the hydrogen bonding interaction between the cis‐enamide substrate and the manganese based oxygen transferring species.

Herein, we report the direct selective C−H lactonization of fatty acids (C5−C16), catalyzed by manganese(II) complexes bearing bis-amino-bis-pyridine ligands. The catalyst system uses the environmentally benign hydrogen peroxide as oxidant and exhibits high efficiency (100−200 TON), providing under optimized conditions γ-lactones in 60−90% yields. Remarkably, by changing the reaction conditions, the oxidation of hexanoic acid can be diverted toward formation of δcaprolactone in up to 67% yield. Furthermore, the possibility of obtaining (ω-1)-hydroxy derivatives from linear C7−C10 acids in up to 48% yields has been demonstrated.