The Lewis acidic nature of organoboranes (BR 3 ) is well understood and makes them reactive towards nucleophilic species, and their ability to participate in free-radical processes widely expands their synthetic use in 1966 [ 1 ]. Trialkylboranes (BR 3 ) can easily undergo bimolecular homolytic substitution (S H 2) at the boron atom  to generate alkyl radicals (R ● ) and substitution takes place at the boron atom under the oxygen atmosphere conditions, instead of heat or light for radical generation, is highly desirable in chemical synthesis, particularly for the formation of thermally unstable products. As shown in Scheme 1A. Trialkylboranes readily undergo S H 2 reactions because the formation of stronger B–X (e.g. B–O) bonds via substitution is highly exothermic [ 2 ]. The BDEs (B–C) of BMe 3 , BEt 3 , BnPr 3 , BiPr 3 , and BnBu 3 range from 344 to 354 kJ mol -1 at 298 K, while their typical auto-oxidation products, B(OH) 3 , B(OMe) 3 , and B(OEt) 3 , have BDEs (B–O) r...