Lewis base-stabilized difluoroboranes 2, 4-pyr and 4-ⁱPr, having an oxazoline- or amine-tethered amide ligand, were synthesized and fully characterized. The treatment of 2 with KC₈ led to its complete consumption, and the rearranged product 5-H, probably originating from C–O bond cleavage and B–O bond formation, could be isolated as a major Dip-containing product in 18% yield. From deuterium labelling experiments and diffusion control reactions, the formation of 5-H could be explained by a radical mechanism. The reduction of 4-pyr and 4-ⁱPr using one-electron reducing agents also gave the rearranged products 13-pyr and 13-ⁱPr in 21 and 19% yields, respectively, via C–N bond cleavage and B–N bond formation. The mechanism for the formation of 13-pyr and 13-ⁱPr is suggested to contain a benzylic radical intermediate.