Manganese(III) 5,15-diazaporphyrins: Synthesis, properties, and catalytic use for benzylic C-H fluorination

Fluorination of sp(3) C-H bonds has attracted considerable attention as a promising method for the synthesis of organofluorine compounds. Manganese porphyrins have been extensively investigated as catalysts in the fluorination of saturated sp(3) C-H bonds. Recently, we have found iron(III) 5,15-diazaporphyrins, which are porphyrin analogues with imine-type sp(2)-hybridized nitrogen atoms at the meso-positions, showing high catalytic performance in the oxidation of sp(3) C-H bonds. Here we disclose the synthesis, structure, and electronic properties of manganese(III) 5,15-diazaporphyrins. We demonstrate that chloromanganese(III) 5,15-diazaporphyrins exhibit high catalytic performance due to their intrinsic electron-deficient nature. Fluorination of sp(3) C-H bonds has attracted considerable attention as a promising method for the synthesis of organofluorine compounds. Manganese porphyrins have been extensively investigated as catalysts in the fluorination of saturated sp(3) C-H bonds. Recently, we have found that iron(III) 5,15-diazaporphyrins, which are porphyrin analogues with imine-type sp(2)-hybridized nitrogen atoms at the meso-positions, showed high catalytic performance in the oxidation of sp(3) C-H bonds. Here we disclose the synthesis, structure, and electronic properties of manganese(III) 5,15-diazaporphyrins. We also demonstrate the catalysis of chloromanganese(III) 5,15-diazaporphyrins for benzylic fluorination.