Direct ortho‐Selective Amination of Naphthols with Nitroarenes through Transfer‐Hydrogenation

Hydrogen atom transfer from commonly used solvents to nitroarenes occurred. Such solvents required C(sp 3 )H‐C(sp 3 )H bond adjacent to oxygen atoms, such as 1,4‐dioxane, tetrahydrofuran, alkanol, ethylene glycol, glycerol and bis(2‐methoxyethyl) ether. The transformation was transition‐metal free and the reduced nitroarenes were trapped by naphthols and their analogues at ortho ‐position. The protocol provided a favourable and efficient route to access ortho ‐arylaminonaphthols and a possible mechanism is depicted.