View article

Bioorthogonal C−H allylation with ample scope was accomplished through a versatile manganese(I)‐catalyzed C−H activation for the late‐stage diversification of structurally complex peptides. The unique robustness of the manganese(I) catalysis manifold was reflected by full tolerance of sensitive functional groups, such as iodides, esters, amides, and OH‐free hydroxy groups, thereby setting the stage for the racemization‐free synthesis of C−H fused peptide hybrids featuring steroids, drug molecules, natural products, nucleobases, and saccharides.