Radical‐Induced 1,2‐Migrations of Boron Ate Complexes

1,2‐Boron ate rearrangements represent a fundamental class of transformations to establish new C−C bonds while retaining the valuable boron moiety in the product. In established ionic processes, the boron ate complex is activated by an external electrophile to induce a 1,2‐migration from boron to an adjacent sp3 or sp2 carbon atom. Recently, two complementary radical polar crossover approaches have been explored for both classes, 1,2‐migrations to sp2 and sp3 carbon centers. This review describes the general concepts in this emerging research field and summarizes recent developments of radical‐induced 1,2‐migrations from boron to carbon.