Radical‐Promoted C−C Bond Cleavage: A Deconstructive Approach for Selective Functionalization

Just as “Deconstructivism” appeared as a novel movement in architecture in the 1980s, deconstructive approaches have recently emerged as excellent strategies for scaffold hopping modifications in chemistry. The deconstruction and functionalization of cyclic molecules mainly involves the cleavage of the carbon–carbon (C−C) bond followed by the construction of new bonds. The cleavage of inert C−C single bonds, especially in unstrained cycles, and their subsequent functionalization is still one of the most sought‐after challenges in chemistry. In this vein, radical‐mediated strategies provide an excellent approach for achieving this aim. This minireview is an outline of the history of homolytic cleavage and highlights the recent advances in exploring new chemical space by deconstructive functionalization. The deconstruction and functionalization of cyclic molecules mainly involves the cleavage of a C−C bond followed by the construction of new bonds. The cleavage of inert C−C bonds and their subsequent functionalization is one of the greatest challenges in chemistry. This Minireview gives an outline of the history of homolytic cleavage and highlights recent advances in exploring new chemical space by deconstructive functionalization.