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.