In this talk, a tandem protocol for the synthesis of cycloalkenes based on the merger of rhodium catalysis and traceless pericyclic rearrangement will be presented. This strategy enables alkyne-tethered N-sulfonylhydrazones and organoboronic acids to undergo a cascade of addition―cyclization―rearrangement reactions to provide cycloalkene products. Mechanistic studies suggest that the process is commenced by the rhodium-catalyzed addition―cyclization and completed with the retro-ene reaction of an allylic diazene intermediate. The novel transformation can be rendered asymmetric by using chiral diene ligands for the rhodium catalyst, whereby enantioselective addition to the C=N bond establishes the C―N stereocenter whose chirality is transferred to an allylic C―H center via suprafacial rearrangement.