Abstract
Indole dearomatization has been achieved via radical hydroarylation. Under mild photoredox conditions, a range of indole derivatives undergo hydroarylation to form 2-arylindoline products. Mechanistically, radical termination occurs primarily via stepwise reduction/protonation, with a small contribution from concerted hydrogen atom transfer. This mechanistic understanding prompted the extension of this reactivity to benzenoid dearomatization. This work formed the foundation of our program, which utilizes reductive radical-polar crossover to drive highly selective dearomatization pathways.