Catalyst‐Free Nitrative Dearomatization of 2‐Naphthols with <i>tert</i> ‐Butyl Nitrite through Radical Coupling

Abstract An efficient and direct approach of dearomatizing nitration of α ‐substituted β ‐naphthols with tert ‐butyl nitrite has been successfully developed under mild conditions. This innovative catalyst‐free method enables the synthesis of cyclic ketones featuring an all‐substituted carbon center in good yields. The mechanistic studies indicate that the formation of the C─N bond is achieved through radical–radical coupling.