Metal-free C-H amination of unactivated hydrocarbons with sulfonylimino-λ(3)-bromanes generated in situ from (diacetoxybromo)benzene.

A simple method for direct metal-free C-H amination of unactivated hydrocarbons using easy-handling diacetoxy-λ(3)-bromane and triflylamide or sulfamate esters was developed. The high 2°/3° regioselectivities and deuterium isotope effects suggest a concerted organonitrenoid transition state, analogous to C-H amination with N-triflylimino-λ(3)-bromane.