Abstract
Rearrangement reactions, one of the most significant transformations in organic chemistry, play an irreplaceable role in improving synthetic efficiency and molecular complexity. Concomitant cleavage and reconstruction of chemical bonds can display the great artistry and the glamour of synthetic chemistry. Over the past century, ionic rearrangement reactions, in particular those involving cationic pathways, have represented most of the research. Alongside the renaissance of radical chemistry, radical-mediated rearrangements have recently seen a rapid increase of attention from the chemical community. Many new radical rearrangements that extensively reveal the migratory behaviour of functional groups have been unveiled in the last decade. This Review provides a comprehensive perspective on the area from the past to present achievements, and brings up the prospects that may inspire colleagues to develop more useful synthetic tools based on radical rearrangements.