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.
Keywords: C−H activation; hybrid peptides; labeling; manganese; peptides.
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