Embracing Triplet Aryl Nitrenes for C-to-N Transmutation of Complex Molecules

Despite significant proof-of-concept advances, aromatic C-to-N replacement reactions remain limitingly substrate-specific and exhibit an overreliance on harsh oxidation methods that preclude their deployment in demanding contexts. Transformations relying on singlet nitrene valence insertion, in particular, have suffered from parasitic intersystem crossing to the triplet spin state, which does not undergo the same rearrangement. We report herein a reaction that productively engages triplet aryl nitrenes for C-to-N replacement with broad scope under mild conditions, enabling its application to complex, sensitive natural products.