Cleavage of unactivated bonds, such as amides, often requires challenging reaction conditions with strong acids and bases, and the tolerance of functional groups is limited. Therefore, the development of cleavage reactions for unactivated bonds under mild reaction conditions is essential. Herein, I report our recent developments in the cleavage of unactivated bonds under mild conditions. We achieved cleavage of unactivated amides, carbamates, ureas, and esters, as well as chemoselective cleavage of directing groups. Furthermore, we conducted mechanistic studies and found that these reactions proceed through the stabilization of addition intermediates.