The activation of inert C(sp~3)–H bonds with control of reactivity and selectivity is one of the central topics in chemical sciences. In this context, alkoxy radical-mediated 1,5- hydrogen atom transfer allows the regioselective transformation of inert C(sp~3)–H bonds to access functionalized molecules which would otherwise be inaccessible. Although some preliminary but elegant results have been disclosed, this chemistry remains challenging and largely underexploited for the following reasons: (1) the bond dissociation energy of O–H bonds is...