Modular Access to Silicon‐Containing Amino Acids and Peptides by Cobalt Catalysis

A regioselective cobalt‐catalyzed three‐component silylamidation that rapidly and reliably incorporates dioxazolones and silylzinc pivalates into unconjugated alkenyl amides is disclosed. Notably, the unique power of this protocol is demonstrated by the possibility of achieving peptide ligation using peptide‐containing dioxazolones or alkenyl amides as the coupling partners. Moreover, this approach is distinguished by its mild condition, synthetic simplicity, and ample scope, thus providing a new platform for modular access to silicon‐containing amino acid derivatives and peptides.