Synergistic Heterobimetallic Manifold for Expedient Manganese(I)‐Catalyzed C−H Cyanation

The manganese‐catalyzed cyanation of inert C?H bonds was achieved within a heterobimetallic catalysis regime. The manganese(I) catalysis proved widely applicable and enabled C?H cyanations on indoles, pyrroles and thiophenes by facile C?H manganesation. The robustness of the manganese catalyst set the stage for the racemization‐free C?H cyanation of amino acids with excellent levels of positional and chemo selectivity by the new cyanating agent NCFS. Experimental and computational mechanistic studies provided strong support for a synergistic heterobimetallic activation mode, facilitating the key C?C formation.