Chemoselective N-H insertion catalysed by a de novo carbene transferase.

The ability to perform organic reactions with chemoselectivity is of critical importance in synthesis. Recently we reported that a de novo carbene transferase, a tetra‐α‐helical c‐type heme‐containing protein, C45, is proficient at N‐H insertion reactions, proceeding via the intermolecular transfer of a metallocarbenoid intermediate into the N‐H σ‐bond to form a new N‐C σ‐bond. Here we demonstrate that C45 can also catalyse N‐H insertion reactions chemoselectively, even when the substrate contains an unprotected hydroxyl group.