Late‐Stage Diversification by Manganese‐Catalyzed C–H Activation: Access to Acyclic, Hybrid and Stapled Peptides

The chemo‐selective late‐stage diversification of structurally complex peptides was accomplished by versatile manganese(I)‐catalyzed C–H activation in terms of bioorthogonal C–H allylation with ample scope. The unique robustness of the manganese(I) catalysis manifold was reflected by fully tolerating sensitive functional groups, such as iodides, esters, amides and OH‐free hydroxyl groups, setting the stage for racemization‐free C–H fusion peptide hybrids featuring steroids, drug molecules, natural products, nucleobases and saccharides.

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